JPS59144737A - Glycerol derivative - Google Patents
Glycerol derivativeInfo
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- JPS59144737A JPS59144737A JP1926483A JP1926483A JPS59144737A JP S59144737 A JPS59144737 A JP S59144737A JP 1926483 A JP1926483 A JP 1926483A JP 1926483 A JP1926483 A JP 1926483A JP S59144737 A JPS59144737 A JP S59144737A
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Abstract
Description
【発明の詳細な説明】 本発明は新規なりリセＯ−ル誘導体に関する。[Detailed description of the invention] The present invention relates to novel lyse O-l derivatives.
本発明のクリｔｏ−ル誘導体は下記一般式（Ｉ）で表わ
される。The Kritol derivative of the present invention is represented by the following general formula (I).
（式中Ｒ１はニド０基又はアミノ基を示し、Ｒ２及びＲ
３は夫々水素原子、アル＋ル基、シク□アル士ル基、テ
トラハイド０ピラニル基、テトラハイドロフルフリル基
又はフェニル基を示す。）上記一般式（Ｉ）中、Ｒ２及
びＲ３で表わされるアル＋ル基としては、炭素数１〜６
のアル＋ル基、例えば、メチル、エチル、づ０ピル、イ
ソづロビル、づチル ／＜ジチル、へ＋シル基等を、シ
ク〇アル＋ル基としては、炭素数５〜７のシフ０アル十
ル基、例えばシフ０ベシチル、シフ０へ＋シル、シフＤ
へづチル基等を、それぞれ例示できる。又、Ｒ□で表わ
されるニトロ基又はアミノ基はべ、７′１！シ環上の任
意の位置に置換しうる。(In the formula, R1 represents a nido group or an amino group, R2 and R
3 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a tetrahydropyranyl group, a tetrahydrofurfuryl group, or a phenyl group, respectively. ) In the above general formula (I), the alkyl group represented by R2 and R3 has 1 to 6 carbon atoms;
Examples of alkyl groups such as methyl, ethyl, pyl, isodurobyl, butyl/<dityl, and hexyl groups include cyclyl groups having 5 to 7 carbon atoms. Al-10 groups, e.g. Schif 0 besityl, Schif 0 to + syl, Schif D
Examples include heptyl group and the like. Also, the nitro group or amino group represented by R□ is 7'1! It can be substituted at any position on the cy ring.
本発明の上記一般式（Ｉ）で表わされるクリセ〇−ル誘
導体は、例えば抗アレルｆ−作用を有する一般式
０Ｂ３
（Ｕ）
（式中Ｘは陰イオシを、Ｒ２及びＲ３は前記と同一の意
味を示す。）
で表わされるスルホニウム芯導体の製造原料として有用
である。The chrysal derivative of the present invention represented by the above general formula (I) has, for example, the general formula 0B3 (U) having anti-allele f-action (wherein X represents an anion, R2 and R3 are the same as above). It is useful as a raw material for manufacturing sulfonium core conductors represented by
一般式（ＴＩ）で表わされるスルホニウム誘導体の製造
方法については、後記参考例において具体的に述べる。The method for producing the sulfonium derivative represented by the general formula (TI) will be specifically described in Reference Examples below.
本発明の一般式（Ｉ）で表わされるクリ上０−ル誘導体
は、その有するＲ□、Ｒ２及びＲ３の種類に応じて、夫
々以下に示す反応経路に従い製造される。The krylic 0-ol derivative represented by the general formula (I) of the present invention is produced according to the reaction route shown below, depending on the types of R□, R2 and R3 contained therein.
〈Ｒ□がニトロ基及びＲ３が水素原子である本発明化合
物（１，ｚ）の製造〉
一般式（ＩＣｔ）で表わされる本発明化合物は、次に示
す三種の製造方法により製造される。<Production of the compound of the present invention (1,z) in which R□ is a nitro group and R3 is a hydrogen atom> The compound of the present invention represented by the general formula (ICt) is produced by the following three production methods.
■ Ａ法
（■旧
（Ｃ）
（式中Ｒ２は前記と同一の意味を示す。）すなわち、一
般式（ＴＩＴ）で表わされるアル＋レシオ十サイド誘導
体に、一般式（ＴＶ）で表わされるアルコール誘導体を
反応させることにより一般式（１，ｚ）で表わされる本
発明化合物を得る。■ Method A (■ Old (C) (In the formula, R2 has the same meaning as above.) In other words, an alcohol represented by the general formula (TV) is added to the al+ratio tenside derivative represented by the general formula (TIT). The compound of the present invention represented by the general formula (1, z) is obtained by reacting the derivative.
該反応はベンゼシ、トルニジ、＋シレシ、アセト二１〜
リル、ニドＤメタン等の溶媒の存在下又は無溶媒下で行
なわれる。式（Ｔ［Ｔ）の化合物と式（ＩＶ）の化合物
との使用割合は、式（ｍ）の化合物Ｉｔルに対し、式（
ＩＶ）の化合物を１〜１０倍モル程度とすればよく、反
応温度は通常約５０℃〜１５０℃とすればよい。又、反
応系内に濃硫酸等の鉱酸を添加することにより、反応を
促進させることができる０
■ Ｂ法
（式中Ｒ２は前記と同一の意味を示す。）また、ニトロ
フェノールに、一般式（Ｖ）で表わされる化合物を反応
させることによっても、一般式（■α）で表わされる本
発明化合物を得ることができる。該反応はベコ１１！シ
、トルニジ、＋シレシ、テトラハイドロフラジ、ジオ十
サシ等の反応に関与しない溶媒の存在下、又は無溶媒下
で行なわれる。ニトロフェノールと式（Ｖ）の化合物と
の使用割合は、通常ニトロフェノールｉ’ｅルに対１７
式（Ｖ）の化合物を１〜２倍ｔル程度とすればよく、反
応温度は、室温から１００℃程度とされる。該反応にお
いては、反応系内に例えばビリジシ、炭酸カリウム等の
塩基を添加することにより、反応を促進させることがで
きる。The reaction is benzene, tornidi, +shireshi, acetoni1~
The reaction is carried out in the presence of a solvent such as methane or methane, or in the absence of a solvent. The ratio of the compound of formula (T[T) and the compound of formula (IV) to be used is as follows:
The amount of the compound IV) may be about 1 to 10 times the molar amount, and the reaction temperature may be generally about 50°C to 150°C. In addition, the reaction can be accelerated by adding a mineral acid such as concentrated sulfuric acid into the reaction system. The compound of the present invention represented by the general formula (■α) can also be obtained by reacting the compound represented by the formula (V). The reaction is Beko 11! The reaction is carried out in the presence of a solvent that does not participate in the reaction, such as silica, tornidi, +shireshi, tetrahydroflage, dioxazashi, etc., or in the absence of a solvent. The ratio of nitrophenol to the compound of formula (V) is usually 17 to nitrophenol.
The amount of the compound of formula (V) may be about 1 to 2 times the amount, and the reaction temperature is from room temperature to about 100°C. In this reaction, the reaction can be accelerated by adding a base such as viridis or potassium carbonate into the reaction system.
■ Ｃ法
（式中Ｒ２は前記と同一の意味を示す。）更に、ニトロ
フェノールに、一般式（Ｖｌ）で表わされる化合物を、
アルカリ金属の水酸化物の存在下に反応させることによ
っても、一般式（■ｃＬ）で表わされる本発明化合物を
収得できる。該反応は、本反応自体に影響を与えない、
メタノール、エタノール等のアルコール類、アセ１ヘシ
、ジオ十サン等の有機溶媒、水、又は前記有機啓媒と水
の混合溶媒中で行なわれる。ここで用いられるアルカリ
金属の水酸化物としては、例えば水酸化ナトリウム、水
酸化カリウム等が挙げられる。ニトロフェノールと式（
ＶＩ）の化合物との使用割合は通常ニド０フエノールＩ
Ｅルに対し、式（至））の化合物を１〜２倍ｔルとすれ
ばよく、アルカリ金属の水酸化物もまたニトロフェノー
ルｌモルに対し約１〜２倍ｔルとなる量で用いられる。■ Method C (In the formula, R2 has the same meaning as above.) Furthermore, a compound represented by the general formula (Vl) is added to nitrophenol,
The compound of the present invention represented by the general formula (■cL) can also be obtained by reacting in the presence of an alkali metal hydroxide. The reaction does not affect the reaction itself,
The reaction is carried out in an alcohol such as methanol or ethanol, an organic solvent such as acetate, dioxane, water, or a mixed solvent of the organic solvent and water. Examples of the alkali metal hydroxide used here include sodium hydroxide, potassium hydroxide, and the like. Nitrophenol and the formula (
The ratio of compound VI) to be used is usually nido 0 phenol I
The amount of the compound of formula (to)) may be 1 to 2 times the amount per mole of nitrophenol, and the alkali metal hydroxide may also be used in an amount of about 1 to 2 times the amount per mole of nitrophenol. It will be done.
反応温度は通常、５０℃から１００℃である。The reaction temperature is usually 50°C to 100°C.
〈Ｒ□がアミノ基及びＲ３が水素原子である本発明化合
物ＣＩＡ）の製造〉
（■α）
（式中Ｒ２は前記と同一の意味を示す。）一般式（Ｉｈ
）で表わされる本発明化合物は、上記反応式に示したよ
うに、一般式（■ｃＬ）で表わされる本発明化合物を、
接触還元することにより製造される。接触還元に使用す
る触媒としては、例えば白金、酸化白金、パラジウム、
酸化パラジウム、パラジウム硫酸バリウム、パラジウム
炭酸カルシウム、パラジウム炭素、酸化ニッケル、ラネ
ーニッケル等が挙げられる。接触還元反応は、本反応に
関与しない溶媒、例えばメタノール、エタノール等のア
ルコール類；テトラハイド０フラジ、ジオ中サシ等のエ
ーテル類；酢酸エチル等のエステル類及びこれら有機溶
媒と水との混合溶媒等を用いて行なわれる。反応は通常
、室温から１００℃の範囲で行なわれる。<Production of the compound CIA of the present invention in which R□ is an amino group and R3 is a hydrogen atom> (■α) (In the formula, R2 has the same meaning as above.) General formula (Ih
) As shown in the above reaction formula, the compound of the present invention represented by the general formula (■cL) is
Produced by catalytic reduction. Examples of catalysts used for catalytic reduction include platinum, platinum oxide, palladium,
Examples include palladium oxide, palladium barium sulfate, palladium calcium carbonate, palladium carbon, nickel oxide, and Raney nickel. The catalytic reduction reaction can be carried out using solvents that do not participate in the reaction, such as alcohols such as methanol and ethanol; ethers such as Tetrahyde 0-Fradi and Dionasashi; esters such as ethyl acetate; and mixed solvents of these organic solvents and water. etc. The reaction is usually carried out at a temperature ranging from room temperature to 100°C.
＜−Ｒ３が水素原子以外の基である本発明化合物（ＩＣ
）及び（Ｉｄ、）の製造〉
（■α）
（ＩＣ）
（Ｉｄ）
（式中Ｒ２は前記と同一の意味を示し、Ｒ４は水素原子
以外のＲ３基、即ちアル＋ル基、シフ０アル牛ル基、テ
トラハイド０ピラニル基、テトラハイド０フルフリル基
又はフェニル基を示す。またＸはハ０ゲシ原子を示す。Compounds of the present invention in which <-R3 is a group other than a hydrogen atom (IC
) and (Id, )> (■α) (IC) (Id) (In the formula, R2 has the same meaning as above, and R4 is an R3 group other than a hydrogen atom, that is, an alkyl group, a shift It represents a cow group, a tetrahydride pyranyl group, a tetrahydride furfuryl group, or a phenyl group. Also, X represents a bald atom.
）
一般式（ＩＣ）及び（Ｉｄ）で表わされる本発明化合物
は、上記反応式に示す方法に従い製造される。) The compounds of the present invention represented by general formulas (IC) and (Id) are produced according to the method shown in the above reaction formula.
即ち一般式（■α）で表わされる本発明化合物に、一般
式（９）で表わされる化合物を、アルカリ金属又はそれ
らの水素化物の存在下に反応させることにより一般式（
ＩＣ）の化合物を得ることができる。That is, by reacting the compound of the present invention represented by the general formula (■α) with the compound represented by the general formula (9) in the presence of an alkali metal or a hydride thereof, the general formula (
IC) can be obtained.
また該一般式（ＩＣ）の化合物を、更に接触還元するこ
とにより一般式（Ｉｄ）の化合物を得ることができる。Further, the compound of general formula (Id) can be obtained by further catalytic reduction of the compound of general formula (IC).
一般式（■）において、Ｘで表わされるハロゲン原子と
しては塩素、臭素又はヨウ素原子を例示することができ
る。In the general formula (■), the halogen atom represented by X can be exemplified by chlorine, bromine or iodine.
一般式（ＩＣ）で表わされる本発明化合物を製造する反
応において、使用する溶媒としては、反応に関与しない
ものである限り特に限定されないが、具体的にはべ′Ｊ
ｔ！シ、テトラハイド０フラジ、ジオ中サシ等を例示す
ることができる。又、本反応に使用するアルカリ金属又
はそれらの水素化物としては、ナトリウム、カリウム、
水素化ナトリウム、水素化カリウム等が挙げられる。一
般式（■ａ）で表わされる化合物と一般式（Ｖｆｒ）で
表わされる化合物、及びアルカリ金属又はその水素化物
の使用割合は、通常一般式（Ｉα）の化合物１ｔルに対
し、一般式（■）で表わされる化合物及びアルカリ金属
又はその水素化物を、それぞれ１〜２倍ｔル程度とする
のがよく、反応温度は、通常０℃〜８０℃とされるのが
好ましい。In the reaction for producing the compound of the present invention represented by the general formula (IC), the solvent used is not particularly limited as long as it does not participate in the reaction, but specifically,
T! For example, silica, tetrahide 0 flage, geo medium sashimi, etc. In addition, the alkali metals or their hydrides used in this reaction include sodium, potassium,
Examples include sodium hydride and potassium hydride. The proportions of the compound represented by the general formula (■a), the compound represented by the general formula (Vfr), and the alkali metal or its hydride are usually per 1 liter of the compound of the general formula (Iα). ) and the alkali metal or its hydride in an amount of about 1 to 2 times the amount, respectively, and the reaction temperature is usually preferably 0°C to 80°C.
また一般式（Ｉｃｌ）で表わされる本発明化合物は、」
二紀の製造方法によって得られた一般式（■ｃ）で表わ
される化合物を接触還元することにより製造することが
できる。接触還元の反応条件は一般式（Ｉｓ）の化合物
の製造において述べた条件と同一とすることができる。The compound of the present invention represented by the general formula (Icl) is
It can be produced by catalytic reduction of the compound represented by the general formula (■c) obtained by Niki's production method. The reaction conditions for the catalytic reduction can be the same as those described for the production of the compound of general formula (Is).
このようにして各反応行程に従い製造された本発明化合
物は、通常の分離精製手段、例えば蒸留、再結晶、クロ
マトクラフィー等により単離することができる。The compounds of the present invention thus produced according to each reaction step can be isolated by conventional separation and purification means such as distillation, recrystallization, chromatography, etc.
次に本発明を具体的に説明するため、本発明化合物から
抗アレル千−作用を有する化合物の合成例を参考例とし
て挙げ、次いで本発明化合物の製造例を実施例として挙
げる。尚参考例及び実施例中の化合物番号は、後記表１
中の化合物番号に対応するものである。Next, in order to specifically explain the present invention, an example of synthesis of a compound having an antiallergic effect from the compound of the present invention will be given as a reference example, and then an example of the production of the compound of the present invention will be given as an example. The compound numbers in Reference Examples and Examples are shown in Table 1 below.
This corresponds to the compound number in the table.
参考例 １
２−Ｃ４−Ｃ３−エト中シー２−ハイドＤ＋シづ０ヒル
オ士シ）フェニルカルバ七イル）エチルジメチルスルホ
ニウム ｐ−トルニジスルホネートの合成
４−（３−エト＋シー２−ハイドＯ士シづ０ヒルオ＋シ
）アニソ、７（化合物２０）１５．２Ｆ（０，０７２０
七ル）とトリエチルアミン１４．６ｆ（０，＋４４′ｆ
、ル）とをジメチルホルムアミド４０４に溶解し、これ
に水冷下、３−メチルメルカづトづロヒオニルクＯライ
ド１１ ？ （０，０７９２ｆニル）を滴下する。室温
で１２時間、次いで４０〜５０℃で１時間攪拌後、濃縮
し、水１００ ｍ、ｌを加え、クロロホルム１００ｍノ
で抽出する。このり００ホルム溶液を１規定塩酸５０ｍ
１．飽和炭酸ナトリウム水溶液５３ｍ１及び水１００ｍ
Ａ！で順次洗浄し、クロロホルム溶液を濃縮する。これ
にエーテル２０ｄを加え、水冷し、析出した結晶を流過
し、乾燥して、ｍ１７９〜８１℃の２−［４−（３−１
１−＋シー２−ハイド０＋シづ口ごルオ＋シ）フェニル
カルバ七イル〕エチルメチルサルファイド１５．２ｆを
得た。Reference Example 1 Synthesis of 2-C4-C3-ethyl 2-hyde D + 2-hide O) phenylcarb7yl)ethyldimethylsulfonium p-tornidisulfonate 4-(3-eth + 2-hyde O Shishizu0 Hiruo + Shi) Aniso, 7 (Compound 20) 15.2F (0,0720
7l) and triethylamine 14.6f (0,+44'f
, 1) were dissolved in dimethylformamide 404, and 3-methylmerca was added to the dichlorohionyl chloride 11? under water cooling. (0,0792fnyl) is added dropwise. After stirring at room temperature for 12 hours and then at 40-50°C for 1 hour, the mixture is concentrated, added with 100 ml of water, and extracted with 100 ml of chloroform. Add 00 form solution to 50ml of 1N hydrochloric acid.
1. Saturated sodium carbonate aqueous solution 53ml and water 100ml
A! and then concentrate the chloroform solution. 20 d of ether was added to this, cooled with water, the precipitated crystals were filtered out, dried, and 2-[4-(3-1
15.2f of ethyl methyl sulfide was obtained.
次に上記で得られた化合物２ Ｏｆ （０，０６３９ｔ
ル）に、Ｐ〜トルエシスルホシ酸メチルエステル２３．
８９ （０，＋２８七ル）を加え、室温で４日間放置す
る。この溶液にエーテル２００ｍ１を加え油状物を分離
し、エタノール−エーテルで精製して、ｍＰ７２〜７３
℃の標記化合物２７Ｆ（収率８４．７％）を得た。Next, compound 2 Of (0,0639t
23.
89 (0,+287 l) and leave at room temperature for 4 days. Add 200 ml of ether to this solution to separate the oil, purify with ethanol-ether, and mP72-73
C. The title compound 27F (yield 84.7%) was obtained.
元素分析 ｃ２３ｘ３３ｎｏ６ｓ２（４９９，６４とし
て）ＨＮ
計算値（％） ５５．２Ｂ ６．６６ ２．
８０測定値（チ） ５５．１６ ６，７２ ２
．９６実施例 ｌ
タリシジルＰ−二１〜ロフェニルエーテル４０２に、ル
ーづロバノール２００ｒＲ１’と濃硫酸４滴とを加え、
６時間還流する。過剰のｎ−ｊロバノールを留去し、水
２００ｍ１！を加え、これをり０口ホルム５０ＣＪｍｔ
で抽出する。クロロホルム溶液を水洗後、芒硝で乾燥し
、濃縮する。減圧蒸留し、ｈ、 ｐ。Elemental analysis c23x33no6s2 (as 499,64) HN Calculated value (%) 55.2B 6.66 2.
80 measurement value (ch) 55.16 6,72 2
．． 96 Example 1 To talicidyl P-21 to lophenyl ether 402, add Ruzulovanol 200rR1' and 4 drops of concentrated sulfuric acid,
Reflux for 6 hours. Excess n-j lovanol was distilled off and 200ml of water was added! Add this and add 0 mouth form 50CJmt
Extract with After washing the chloroform solution with water, dry it with Glauber's salt and concentrate. Distilled under reduced pressure, h, p.
１８８〜ｂ
イドＤ＋シー３−”５０ヒルオ士シづＯヒルオ十シ）ニ
ド０ベンゼ′Ｊ（化合物３）３６．４４（収率７０％）
を得た。188-b IdoD+C3-"50HiruoshishizuOhiruojushi) Nido0benze'J (Compound 3) 36.44 (Yield 70%)
I got it.
実施例 ２
実施例Ｉと同様にして、化合物４．６．７及び８を合成
した。Example 2 Compounds 4.6.7 and 8 were synthesized in the same manner as in Example I.
実施例 ３
ニドＤフェノール５０ｒｌ／ｌリシジルフェニルエーテ
ル５３．９ｙとヒリジ、７３滴とを加え、ｌＯ０℃で５
時間攪拌する。反応終了後、冷却し、水２００Ｔｎｌを
加え、クロロホルム５００ｍ１で抽出する。このクロロ
ホルム抽出液を２規定塩酸２００ｍ１，２規定水酸化ナ
トリウム２００ｍＡ！及び水２００ゴで順次洗浄し、芒
硝乾燥後、濃縮する。これをシリカゲルカラムクロマド
グラフイー（展開溶媒：クロロホルム：エタノール＝ｌ
Ｏ：１）で分ｉ精製して４−（２−ハイドロ＋シー３−
フェノ＋シづ０ヒルオ十シ）ニトロベンゼン（化＆物９
）８６．６Ｆ（８３％）を得た。Example 3 Add Nido D phenol 50 rl/l lycidyl phenyl ether 53.9y and Hiriji 73 drops and heat at 100°C for 5
Stir for an hour. After the reaction is completed, the mixture is cooled, 200 Tnl of water is added, and the mixture is extracted with 500 ml of chloroform. This chloroform extract was mixed with 200ml of 2N hydrochloric acid and 200mA of 2N sodium hydroxide! and 200 g of water, dried with sodium chloride, and concentrated. This was subjected to silica gel column chromatography (developing solvent: chloroform: ethanol = l
4-(2-hydro + C3-
pheno+shizu0hiruojushi) nitrobenzene (chemical & thing 9
) 86.6F (83%) was obtained.
実施例 ４ 実施例３と同様にして化合物ｌ及び５を合成した。Example 4 Compounds 1 and 5 were synthesized in the same manner as in Example 3.
実施例 ５
水酸化ナトリウム１８．５ｒを９０％エタノール５００
ｄに溶解し、これにニド０フエノール５０１と１−クロ
ル−３−エト＋シづ０パシー２−オール６０１とを加え
、８時間還流する。これを濃縮し、残渣に水２００ｍＡ
’を加え、り００ホルム５００ｍ１で抽出する。このり
ＯＯホルム抽出液を水洗し、芒硝乾燥後濃縮する。減圧
蒸留してり、 ｐ。Example 5 Sodium hydroxide 18.5r 90% ethanol 500ml
To this were added 501 liters of nidophenol and 601 liters of 1-chloro-3-eth+hydrophenol 2-ol, and the mixture was refluxed for 8 hours. Concentrate this and add 200 mA of water to the residue.
' and extracted with 500ml of Ri00form. This OO form extract is washed with water, dried with sodium chloride, and concentrated. Distilled under reduced pressure, p.
１７３〜ｂ
ト十シー２−ハイドロ＋シ″Ｊｊｏじルオ＋シ）ニトロ
ベ、７＋！υ（化合物２）６０．６Ｆ（収率７０．２％
）を得た。173-b Toshi 2-Hydro + Shi''Jjo Jiluo + Shi) Nitrobe, 7+!υ (Compound 2) 60.6F (Yield 70.2%
) was obtained.
実施例 ６ 実施例５と同様にして化合物ｌＯ及び１１を合成した。Example 6 Compounds 1O and 11 were synthesized in the same manner as in Example 5.
実施例 ７
水素化ナトリウム２．８７ｆを無水ジメチルホルムアミ
ド１００ｍ／に加え、冷却し、この溶液に、４−（２−
ハイド０＋シー３−づロヒルオ十シづＯピルオ十シ）ニ
トロベンゼン（（ｉ物３）１５．２５Ｆを加え室温で２
時間攪拌する。次に水冷下、づ口ごルアイオタイド５０
２を滴下し、室温で４時間攪拌後、８０〜９０℃で２時
間攪拌する。反応液を濃縮し、水１００Ｔｎｌを加え、
これをりＯＯホルム２００ｍ／で抽出する。このクロロ
ホルム溶液を水洗後、濃縮し、減圧蒸留を行々いり、ｐ
、２０３〜ｂ
３−、；づロピルオ士シづロピルオ＋シ）ニド０ベシゼ
シ（化合物１４）１３．６Ｆ（収率７６．５％）を得た
。Example 7 2.87 f of sodium hydride was added to 100 m of anhydrous dimethylformamide, cooled, and 4-(2-
Add 15.25F of nitrobenzene ((i product 3) to 20% at room temperature
Stir for an hour. Next, under water cooling, Iotide 50
2 was added dropwise, and the mixture was stirred at room temperature for 4 hours, and then at 80 to 90°C for 2 hours. Concentrate the reaction solution, add 100 Tnl of water,
This is extracted with 200 m/ml of OO form. After washing this chloroform solution with water, it was concentrated, distilled under reduced pressure, and
, 203-b 3-,;Zuropyruo-shizuropyruo+shi)nido-Obeshizeshi (Compound 14) 13.6F (yield 76.5%) was obtained.
実施例 ８
実施例７と同様にして化合物１２．１３．１５．１６．
１７及び１８を得た。Example 8 Compounds 12.13.15.16.
17 and 18 were obtained.
実施例 ９
４−（３−エト中シー２−ハイド０牛シづロヒルオ十シ
）ニトロベシゼ、７（化合物２）ｌｏｒをエタノール２
００ゴに溶解し、ｔＯＷパラジウム炭素０．２５９を加
え、室温で圧力２ Ｋｇ ／ ｃｔＡで水素添加する。Example 9 4-(3-ethyl, 2-hide, 0 bovine sulfur hydroxide) nitrobescise, 7 (compound 2)lor in ethanol 2
0.00g, add tOW palladium on carbon 0.259 and hydrogenate at room temperature at a pressure of 2 Kg/ctA.
水素吸収が認められなくなった後、反応液を沢過し、ろ
液よりエタノールを留去し、ベンゼン１０ｄを加え、室
温で放置する。析出した結晶を濾過、乾燥してｍ、ｐ、
８３〜８４℃の４−（３−エト中シー２−ハイドロ＋シ
ー５０ピルオ十シ）アニリシ（化合物２０ ） ８．Ｏ
ｆ （収率９１．４％）を得た。After hydrogen absorption is no longer observed, the reaction solution is thoroughly filtered, ethanol is distilled off from the filtrate, 10 d of benzene is added, and the mixture is allowed to stand at room temperature. The precipitated crystals are filtered and dried to give m, p,
83-84°C 4-(2-hydro in 3-ethyl + 50 pyrohydro)anilisi (compound 20) 8. O
f (yield 91.4%) was obtained.
実施例 ｌＯ
実施例９と同様にして化合物１９．２１．２２．２４〜
２９及び３１−３６を得た。Example lO Compounds 19.21.22.24-
29 and 31-36 were obtained.
実施例 １１
４−（３−づチルオ十シー２−ハイドＯ＋シプロピルオ
士シ）ニトロベンゼン（化合物５）１０Ｖをエタノール
ｌｏｏｍＡ’に溶解し、二酸化白金０．１１を加え、室
温で常圧下水素添加する。３ｔル当量の水素吸収が終っ
た後、反応液を濾過し、ろ液からエタノールを留去し油
状物を得た。この油状物を乾燥して４−（３−づチルオ
＋シー２−ハイドロ＋シづＯヒルオ＋シ）アニリ、７（
化合物２３ ＞ ７．５ Ｆ （収率８４．６チ）を得
た。Example 11 10V of 4-(3-dutyloxy-2-hydro+cypropyloxy)nitrobenzene (compound 5) is dissolved in ethanol roomA', 0.11% of platinum dioxide is added, and hydrogenation is carried out at room temperature under normal pressure. After absorbing 3 tl equivalent of hydrogen, the reaction solution was filtered, and ethanol was distilled off from the filtrate to obtain an oily substance. Dry this oil to give 4-(3-Dutiro+C2-Hydro+ShizuO-Hiruo+Shi)anili, 7(
Compound 23 > 7.5 F (yield 84.6) was obtained.
実施例 １２
４− （２，３−ジメト＋シづＤヒルオ＋シ）ニド０ベ
シゼン（化合物１２）３１’をメタノール２００１ｎｌ
に溶解し、ラネーニッケル０．５ ｆを加え、４０℃で
３５Ｋｒ／ｃｒＩの圧力で水素添加を行々つだ。Example 12 4-(2,3-dimeth+ShizuDhiluo+Shi)nide-0-besizene (Compound 12) 31' was dissolved in 2001 nl of methanol.
0.5 f of Raney nickel was added, and hydrogenation was carried out at 40° C. and a pressure of 35 Kr/crI.
３モル当量の水素の吸収が終った後、反応液を流過する
。Ｐ液からメタノールを留去後、減圧乾燥して油状の４
− （２，３−ジメト＋シづＯじルオ＋シ）アニリン（
化合物３０）２８Ｆ（収率９４．０チ）を得た。After absorption of 3 molar equivalents of hydrogen is completed, the reaction solution is passed through. After distilling methanol off from the P solution, drying under reduced pressure yields oily 4.
- (2,3-dimetho+shizuojiluo+shi)aniline (
Compound 30) 28F (yield 94.0) was obtained.
次に本発明化合物の化学構造、ｈ、 ｐ、又はｍ、ｐ、
をを表Ｉに、そのＮＭＲ分析結果を表２に示す。Next, the chemical structure of the compound of the present invention, h, p, or m, p,
The results are shown in Table I, and the NMR analysis results are shown in Table 2.
表 １ −４８−Table 1 -48-
Claims (1)
３は夫々水素原子、アル牛ル基、シクＯアル＋ル基、テ
トラハイド０じラニル基、テトラハイドロフルフリル基
又はフェニル基を示す。）で表わされるクリセＯ−ル誘
導体。[Claims] ■ General formula (in the formula, R represents a nitro group or an amino group, R2 and R
3 each represents a hydrogen atom, an alkyl group, a cycloalkyl group, a tetrahydranyl group, a tetrahydrofurfuryl group, or a phenyl group. ) A chryse O-ol derivative represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1926483A JPS59144737A (en) | 1983-02-08 | 1983-02-08 | Glycerol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1926483A JPS59144737A (en) | 1983-02-08 | 1983-02-08 | Glycerol derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59144737A true JPS59144737A (en) | 1984-08-18 |
| JPH027583B2 JPH027583B2 (en) | 1990-02-19 |
Family
ID=11994576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1926483A Granted JPS59144737A (en) | 1983-02-08 | 1983-02-08 | Glycerol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59144737A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4655173B2 (en) * | 2000-04-27 | 2011-03-23 | 日立化成工業株式会社 | Method for producing compound having oxetanyl group and hydroxyl group in molecule |
| CN110963953A (en) * | 2019-12-04 | 2020-04-07 | 重庆植恩药业有限公司 | Sulfaast tosilate process impurity I and preparation method and application thereof |
-
1983
- 1983-02-08 JP JP1926483A patent/JPS59144737A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4655173B2 (en) * | 2000-04-27 | 2011-03-23 | 日立化成工業株式会社 | Method for producing compound having oxetanyl group and hydroxyl group in molecule |
| CN110963953A (en) * | 2019-12-04 | 2020-04-07 | 重庆植恩药业有限公司 | Sulfaast tosilate process impurity I and preparation method and application thereof |
| CN110963953B (en) * | 2019-12-04 | 2022-02-18 | 植恩生物技术股份有限公司 | Sulfaast tosilate process impurity I and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH027583B2 (en) | 1990-02-19 |
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