JPS6011710B2 - Dibenzopyran-6-acetic acids and method for producing dibenzopyran-6-acetic acids - Google Patents
Dibenzopyran-6-acetic acids and method for producing dibenzopyran-6-acetic acidsInfo
- Publication number
- JPS6011710B2 JPS6011710B2 JP753276A JP753276A JPS6011710B2 JP S6011710 B2 JPS6011710 B2 JP S6011710B2 JP 753276 A JP753276 A JP 753276A JP 753276 A JP753276 A JP 753276A JP S6011710 B2 JPS6011710 B2 JP S6011710B2
- Authority
- JP
- Japan
- Prior art keywords
- dibenzopyran
- acetic acids
- alkyl group
- lower alkyl
- formulas
- 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
Landscapes
- Pyrane Compounds (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Description
【発明の詳細な説明】
本発明は一般式
（式中、Ｒ，は低級アルキル基を表し、Ｒ２は水素原子
および低級アルキル基を表す）で示されるジベンゾピラ
ン−６−酢酸類及びその製造法に関するものである。Detailed Description of the Invention The present invention provides dibenzopyran-6-acetic acids represented by the general formula (wherein R represents a lower alkyl group, R2 represents a hydrogen atom and a lower alkyl group) and a method for producing the same. It is related to.
その製造法の要旨は次の式によって示される。The gist of the manufacturing method is shown by the following formula.
（式中、Ｒ，及びＲ２は前記と同意義を表す）本発明の
ジベンゾピランー６一酢酸類は、２一（３ーヒドロキシ
フエニル）シクロヘキサノール（０）とケト酸類（ｍ）
とを無触媒、あるいは塩酸、パラトルヱンスルホン酸、
トリクロル酢酸等の触媒の存在下、無溶媒あるいは適当
な溶媒中反応せしめることによって製造される。この際
の溶媒としては、反応に関与しないものならなんでもよ
く、例えばメタノール、エタノール、プロピルアルコー
ル類、ブチルアルコール類、アミルアルコール類等の低
級アルコール類、ベンゼン、トルェン、キシレン等の炭
化水素類が用いられる。また、一般式（ｍ）のケトカル
ボン酸類をそのまま溶媒とすることも出来る。反応温度
は常温から２００ｏｏ程度が好ましい。反応時間は１時
間から３加持間程度である。次に使用するケトカルボン
酸としては、例えばァセト酢酸、プロピオニル酢酸、プ
チリル酢酸およびそのェステル類等であるが、これら上
記化合物に限定されるものではない。また、ジベンゾピ
ラン−６−酢酸ェステル類（Ｗ）をアルカリまたは酸触
媒の存在下加水分解してジベンゾピランー６一酢酸類（
Ｖ）を製造することが出来る。(In the formula, R and R2 represent the same meanings as above) The dibenzopyran-6 monoacetic acid of the present invention is composed of 2-(3-hydroxyphenyl)cyclohexanol (0) and a keto acid (m).
and uncatalyzed, or hydrochloric acid, p-toluene sulfonic acid,
It is produced by reaction in the presence of a catalyst such as trichloroacetic acid without a solvent or in an appropriate solvent. The solvent at this time may be any solvent as long as it does not participate in the reaction, such as methanol, ethanol, lower alcohols such as propyl alcohols, butyl alcohols, and amyl alcohols, and hydrocarbons such as benzene, toluene, and xylene. It will be done. Furthermore, the ketocarboxylic acids of general formula (m) can be used as they are as a solvent. The reaction temperature is preferably from room temperature to about 200 oo. The reaction time is about 1 hour to 3 hours. The ketocarboxylic acids to be used next include, for example, acetoacetic acid, propionyl acetic acid, butyryl acetic acid, and their esters, but are not limited to these compounds. In addition, dibenzopyran-6-monoacetic acids (W) can be hydrolyzed in the presence of an alkali or acid catalyst to produce dibenzopyran-6-monoacetic acids (W).
V) can be produced.
ェステルの加水分解の触媒としては、アルカリ類として
水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、
炭酸カリウム等があり、水あるし、は含水アルコール等
の溶媒中加水分解する。Catalysts for hydrolysis of esters include sodium hydroxide, potassium hydroxide, sodium carbonate,
Potassium carbonate, etc. are hydrolyzed in water, water, alcohol, and other solvents.
また酸触媒としては、塩酸、臭化水素酸および硫酸等が
ある。原料である２一（３ーヒドロキシフェニル）シク
ロヘキサノール（ロ）はシス体およびトランス体が存在
するが、それぞれケトカルボン酸類と反応して、ジベン
ゾピランー６一酢酸類を製造することが出来る。Further, examples of acid catalysts include hydrochloric acid, hydrobromic acid, and sulfuric acid. The raw material 2-(3-hydroxyphenyl)cyclohexanol (b) exists in cis and trans forms, and dibenzopyran-6-monoacetic acids can be produced by reacting with ketocarboxylic acids.
当該化合物のある種のものは、抗炎症作用及び鎮痛解熱
作用を有し、従って当該化合物は医療上の価値を有する
。Certain of the compounds have anti-inflammatory and analgesic and antipyretic properties, and therefore have medical value.
例えば１１２・３・４・傘・ｌｏｂーヘキサハイドロー
６ーハイドロキシカルボニルメチルー６ーメチル−母日
一ジベンゾ〔ｂ・ｄ〕ピランー９ーオールはラツトにお
けるカラゲニン浮腫抑制スクリーニングにおいてフェニ
ルブタゾンの１／２程度の抗炎症作用が認められた。次
に実施例にて本発明を説明するが、これらをもって本発
明は制限されるものではない。実施例 １
１・２・３・４・傘・ｌｏｂ−へキサハイドロー６ーハ
イドロキシカルボニルメチル−６ーメチル−母日一ジベ
ンゾ〔ｂ・ｄ〕ピランー９−オールの製造法‘ａ’２−
（３−ヒドロキシフエニル）シクロヘキサノール１夕、
アセト酢酸エチルェステル２夕、ｐートルヱンスルホン
酸０．３夕およびベンゼン１０の‘の混液を１期時間加
熱還流する。For example, 112.3.4.umbrella.lob-hexahydro-6-hydroxycarbonylmethyl-6-methyl-dibenzo[b.d]pyran-9-ol is 1/2 of phenylbutazone in carrageenan edema suppression screening in rats. Some degree of anti-inflammatory effect was observed. Next, the present invention will be explained with reference to examples, but the present invention is not limited to these examples. Example 1 1, 2, 3, 4, umbrella, lob-hexahydro 6-hydroxycarbonylmethyl-6-methyl-mother's day 1 Method for producing dibenzo[b/d]pyran-9-ol'a'2-
(3-hydroxyphenyl)cyclohexanol 1 night,
A mixture of 2 hours of acetoacetic acid ethyl ester, 0.3 hours of p-toluene sulfonic acid, and 10 hours of benzene was heated under reflux for 1 hour.
溶媒留去後１０％ＮａＯＨ水溶液１ｏｗ‘を加えて、１
００ｑｏで１時間加熱する。袷後水層に１０％ＨＣＩ水
溶液を加え酸性とし、Ｅら○抽出する。Ｅｔ２０層を飽
和ＮａＨＣ０３水溶液で抽出し、水層をＥｔ２０にて洗
浄する。水層を１０％ＨＣＩ水溶液にて酸性とし、再び
Ｅｔぬ抽出する。Ｅｔの層をＮａ夕０４にて乾燥後、溶
媒留去し、残留物をベンゼンより再結晶してｍｐ１７２
〜１７５ｏの無色プリズム晶７００の９（４９％）を得
。元素分析値 Ｃ，幻２ｏ０４
計算値：Ｃ、６９．５４：日、７．３０
実験値：Ｃ、６９．７９；日、７．１６
赤外線吸収スペクトル（ｋＢｒ）
１７２０肌‐１（Ｃ＝０）
核磁気共鳴スペクトル（ＣＤＣ１３）
１．６瓜血（犯、一重線、Ｃ−ＣＨ３）
紫外線吸収スペクトル〔ｎｍ（ｌｏｇご）〕２７８．５
（３．３８）｛ｂ｝ 実施例２で得られるジベンゾピラ
ン−６−酢酸メチルヱステル１夕を１０％ＮａＯＨ水溶
液１０の‘に溶解し、１０００で１時間加熱する。After distilling off the solvent, add 1 ow' of 10% NaOH aqueous solution,
Heat at 00qo for 1 hour. A 10% HCI aqueous solution is added to the aqueous layer after rinsing to make it acidic, followed by extraction. The Et20 layer is extracted with a saturated NaHC03 aqueous solution, and the aqueous layer is washed with Et20. The aqueous layer was made acidic with a 10% HCI aqueous solution and extracted again with Et. After drying the Et layer over Na 04, the solvent was distilled off, and the residue was recrystallized from benzene to obtain mp172.
9 of 700 (49%) colorless prismatic crystals of ~175o were obtained. Elemental analysis value C, illusion 2o04 Calculated value: C, 69.54: day, 7.30 Experimental value: C, 69.79; day, 7.16 Infrared absorption spectrum (kBr) 1720 skin-1 (C=0) Nuclear magnetic resonance spectrum (CDC13) 1.6 Melon blood (crime, singlet, C-CH3) Ultraviolet absorption spectrum [nm (log)] 278.5
(3.38) {b} One hour of dibenzopyran-6-methyl acetate obtained in Example 2 is dissolved in 10 ml of a 10% aqueous NaOH solution and heated at 1000 °C for 1 hour.
冷後１０％ＨＣＩ水溶液にて酸性としてＥｔ２０抽出す
る。Ｅｔ２０層をＮａ２Ｓ０４にて乾燥、溶媒留去して
、残留物をベンゼンより再結晶してｍｐ１７２〜１７５
０の無色プリズム晶０．５７夕（６０％）を得。本品は
ａで得られたものと機器分析データ一が一致した。実施
例 ２
１・２・３・４・傘・ｌｏｂーヘキサハイドロ−６ーメ
トキ．シカルボニルメチルー６ーメチルー母日一ジベン
ゾ〔ｂ・ｄ〕ピランー９−オールの製造法実施例１で得
られたジベンゾピラソー６−酢酸１夕をＭｅＯＨ２０奴
に溶解し、塩酸ガスを飽和して、２時間加熱還流する。After cooling, the mixture was acidified with a 10% HCI aqueous solution and extracted with Et20. The Et20 layer was dried with Na2S04, the solvent was distilled off, and the residue was recrystallized from benzene to give mp172-175.
0.57 colorless prismatic crystals of 0.0 (60%) were obtained. The instrumental analysis data for this product matched that obtained in step a. Example 2 1.2.3.4.Umbrella・lob-hexahydro-6-methoxy. Dibenzopyrazo-6-acetic acid obtained in Example 1 was dissolved in 20 g of MeOH and saturated with hydrochloric acid gas. , and heat to reflux for 2 hours.
反応後溶媒留去し、無色カラメル状物１．０夕（９５％
）を得。赤外線吸収スペクトル（ｋＢｒ）
１７３０肌‐１（Ｃ＝０）
３４００肌‐１（〇Ｈ）
核磁気共鳴スペクトル（ＣＤＣ１３）
１．５弦伽（細、一重線、Ｃ−Ｃ舷）
３．４劫四（紺、一重線、Ｃ−Ｃ広）After the reaction, the solvent was distilled off to give a colorless caramel-like substance (95%
) obtained. Infrared absorption spectrum (kBr) 1730 skin-1 (C=0) 3400 skin-1 (〇H) Nuclear magnetic resonance spectrum (CDC13) 1.5 string (thin, single line, C-C broadside) 3.4 kalpa 4 (dark blue, single line, C-C wide)
Claims (1)
原子および低級アルキル基を表す）で示されるジベンゾ
ピラン−６−酢酸類。 ２ 式 ▲数式、化学式、表等があります▼ と一般式 Ｒ＿１ＣＯＣＨ＿２ＣＯＯＲ＿２（III） （式中、Ｒ＿１は低級アルキル基を表し、Ｒ＿２は水素
原子および低級アルキル基を表す）で示されるケト酸類
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、Ｒ＿１は低級アルキル基を
表し、Ｒ＿２は水素原子および低級アルキル基を表す）
で示されるジベンゾピラン−６−酢酸類の製造法。 ３ 一般式 ▲数式、化学式、表等があります▼ （式中、Ｒ＿１は低級アルキル基を表し、Ｒ＿３は低級
アルキル基を表す）を加水分解す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、Ｒ＿１は低級アルキル基を表す）で示されるジ
ベンゾピラン−６−酢酸類の製造法。[Claims] 1. Dibenzopyran-6- represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a lower alkyl group, R_2 represents a hydrogen atom and a lower alkyl group) Acetic acids. 2 Reacting the formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ with a keto acid represented by the general formula R_1COCH_2COOR_2(III) (in the formula, R_1 represents a lower alkyl group, and R_2 represents a hydrogen atom and a lower alkyl group). There are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. that are characterized by
A method for producing dibenzopyran-6-acetic acids represented by 3 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula characterized by hydrolyzing (in the formula, R_1 represents a lower alkyl group, R_3 represents a lower alkyl group) ▲ Numerical formulas, chemical formulas, tables, etc. A method for producing dibenzopyran-6-acetic acids represented by the formula ▼ (wherein R_1 represents a lower alkyl group).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP753276A JPS6011710B2 (en) | 1976-01-28 | 1976-01-28 | Dibenzopyran-6-acetic acids and method for producing dibenzopyran-6-acetic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP753276A JPS6011710B2 (en) | 1976-01-28 | 1976-01-28 | Dibenzopyran-6-acetic acids and method for producing dibenzopyran-6-acetic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52105174A JPS52105174A (en) | 1977-09-03 |
| JPS6011710B2 true JPS6011710B2 (en) | 1985-03-27 |
Family
ID=11668382
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP753276A Expired JPS6011710B2 (en) | 1976-01-28 | 1976-01-28 | Dibenzopyran-6-acetic acids and method for producing dibenzopyran-6-acetic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6011710B2 (en) |
-
1976
- 1976-01-28 JP JP753276A patent/JPS6011710B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52105174A (en) | 1977-09-03 |
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