JPS63210289A - Production of 2-(nitrophenyl) or 2-(nitrophenyl)-2-substituted ethanols - Google Patents
Production of 2-(nitrophenyl) or 2-(nitrophenyl)-2-substituted ethanolsInfo
- Publication number
- JPS63210289A JPS63210289A JP62042803A JP4280387A JPS63210289A JP S63210289 A JPS63210289 A JP S63210289A JP 62042803 A JP62042803 A JP 62042803A JP 4280387 A JP4280387 A JP 4280387A JP S63210289 A JPS63210289 A JP S63210289A
- Authority
- JP
- Japan
- Prior art keywords
- nitrophenyl
- formula
- ethanols
- reaction
- paraformaldehyde
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- -1 2-(nitrophenyl)-2-substituted ethanols Chemical class 0.000 title claims 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229930040373 Paraformaldehyde Natural products 0.000 claims abstract description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims abstract description 6
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 18
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims 1
- 125000006501 nitrophenyl group Chemical group 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- 235000019441 ethanol Nutrition 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 150000005181 nitrobenzenes Chemical class 0.000 abstract description 4
- SLRIOXRBAPBGEI-UHFFFAOYSA-N 2-(2-nitrophenyl)ethanol Chemical class OCCC1=CC=CC=C1[N+]([O-])=O SLRIOXRBAPBGEI-UHFFFAOYSA-N 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000002904 solvent Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- HFZKOYWDLDYELC-UHFFFAOYSA-N 1,2-dimethyl-4-nitrobenzene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1C HFZKOYWDLDYELC-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- FLKQZNFLWOPRFX-UHFFFAOYSA-N 2-(2-chloro-6-nitrophenyl)ethanol Chemical compound OCCC1=C(Cl)C=CC=C1[N+]([O-])=O FLKQZNFLWOPRFX-UHFFFAOYSA-N 0.000 description 1
- 101100448208 Human herpesvirus 6B (strain Z29) U69 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003205 fragrance Substances 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- KEBHLNDPKPIPLI-UHFFFAOYSA-N hydron;2-(3h-inden-4-yloxymethyl)morpholine;chloride Chemical compound Cl.C=1C=CC=2C=CCC=2C=1OCC1CNCCO1 KEBHLNDPKPIPLI-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLZLOWPYUQHHCG-UHFFFAOYSA-N nitromethylbenzene Chemical class [O-][N+](=O)CC1=CC=CC=C1 VLZLOWPYUQHHCG-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
従来の技術
２−にトロフェニル）エタノール類は高分子物質、染料
、農薬、高分子安定剤、感光材料、香料ならびに医薬、
農薬の中間体として有用な化合物である。DETAILED DESCRIPTION OF THE INVENTION Prior art 2-Trophenyl) Ethanols are used as polymeric substances, dyes, agricultural chemicals, polymeric stabilizers, photosensitive materials, fragrances, and pharmaceuticals.
It is a compound useful as an intermediate for agricultural chemicals.
２−にトロフェニル）エタノール類ノ製造方法としては
、例えばＡｃｔａ、 Ｃｈｅｍｉｃａ、５ｃａｎｄｉｎ
ａｖｉｃａ。Examples of methods for producing ethanol (2-trophenyl) include Acta, Chemica, 5candin
avica.
２１巻７１８ページ（１，９６７年）、同誌２１巻１９
６７ページ（１９６７年）にＢ、 Ｗｅｓｓｅｌｃｎ等
によってニトロトルエン類をＤＭＳＯ中テ（ＣＨ２０）
ｎ（ｎは整数）とＥｔｏＮａ 、 ｔ−ＢｕＯＫのよう
な金属アルコラードの存在下に反応させる方法が提案さ
れている。又、１９８６年日本化学会春季大会予稿集■
、１４８３ページ２ＸＯ３には電解反応を用いる合成法
が報告されている。Volume 21, page 718 (1,967), same magazine volume 21, page 19
On page 67 (1967), nitrotoluenes were dissolved in DMSO (CH20) by B. Wesselcn et al.
A method has been proposed in which the reaction is carried out in the presence of n (n is an integer) and a metal alcoholade such as EtoNa or t-BuOK. Also, Proceedings of the 1986 Spring Meeting of the Chemical Society of Japan■
, p. 1483, 2XO3, a synthesis method using an electrolytic reaction is reported.
発明が解決しようとする問題点
前記した方法は工業的に充分満足いく結果を与えていな
い。例えばＢ、 Ｗｅｓｓｅｌｅｎ等の方法は収出が低
くかつ高価で取扱いに特別の注意が必要な金属アルコラ
ードを用いている。又、電解反応を用いる方法は高収高
で目的物を得ることができるが複雑な陽、陰極分離型の
電解装置が必要であり、操作性の面で必ずしも工業的に
有利な製法とはいえない。Problems to be Solved by the Invention The above-mentioned methods have not given industrially satisfactory results. For example, the method of B. Wesselen et al. uses metal alcolades which have low yields and are expensive and require special care in handling. In addition, methods using electrolytic reactions can obtain the desired product with high yields, but require a complicated electrolytic device with separate positive and negative electrodes, and although it is not necessarily an industrially advantageous manufacturing method in terms of operability. do not have.
問題点を解決するための手段
本発明者らは前記したような問題点を解決すを
べく鋭意研究冬型ねた結果、本発明に至ったものである
。即ち本発明はジメチルスルホキシド及ヒ／又はＮ、Ｎ
−ジメチルホルムアミド中、水酸化カリウム又は水酸化
ナトリウムの存在下に式（１）
（式（１）においてＸ、Ｙ及びＺはそれぞれ独立に水素
原子、０１〜４のアルキル基、ニトロ基又はノ・ロゲン
原子を、Ｒは水素原子又はメチル基を表す。但し少なく
とも１個のニトロ基がＣＨ２Ｒ基に対して〇−位又はＰ
−位に置換しているものとする。）
で示されるニトロベンゼン類とバラホルムアルデヒドを
反応させることを特徴とする式（２）（式（２）におい
てＸ、 Ｙ、 Ｚ及びＲは前記と同じ従来ニトロトルエ
ン類のヒドロキシメチル化については前記したＷｅｓｓ
ｅｌｅｎの文献等を含め多くの文献があるがそれらの方
法を追試した結果の概要は第１表に示した通りでいずれ
も工業的見地からみて満足出来るものではない。これに
反して本発明の方法は純度の高い目的物を高収率で与え
るものであり工業的価値が極めて高い。Means for Solving the Problems The present inventors have conducted intensive research in order to solve the above-mentioned problems, and as a result, they have arrived at the present invention. That is, the present invention provides dimethyl sulfoxide and/or N, N
- In dimethylformamide, in the presence of potassium hydroxide or sodium hydroxide, the formula (1) (in formula (1), R represents a hydrogen atom or a methyl group.However, at least one nitro group is at the 〇-position or P
Assume that the substitution is made in the - position. ) Formula (2) characterized by reacting a nitrobenzene represented by
Although there are many documents including the document by Elen, etc., the summary of the results of repeated trials of these methods is shown in Table 1, and none of them are satisfactory from an industrial standpoint. On the other hand, the method of the present invention provides a highly pure target product in a high yield and has extremely high industrial value.
本発明の方法を詳細に説明する。The method of the present invention will be explained in detail.
本発明の方法において原料として用いられる式け）のニ
トロベンゼン類の具体例としては例えば次のものが挙げ
られる。Specific examples of the nitrobenzenes used as raw materials in the method of the present invention include the following.
本発明の方法においてはジメチルスルホキシド（ＤＭＳ
Ｏ）、Ｎ、Ｎ−ジメチルホルムアミド（ＤＭＦ ）又は
これらの混合物が溶媒として用いられるものであり、原
料のニトロベンゼン類が溶媒中に５〜５０（重量％）存
在するように溶媒を使用するのが好ましい。これらの溶
媒はその一部を転化率、目的物の収率低下を招かない範
囲でテトラハイドロフラン、ジクロルメタン、ベンゼン
、トルエン、メタノールのような低沸点有機溶媒で置き
換えることも可能である。In the method of the present invention, dimethyl sulfoxide (DMS
O), N, N-dimethylformamide (DMF) or a mixture thereof is used as a solvent, and the solvent is used so that the raw material nitrobenzene is present in the solvent in an amount of 5 to 50 (wt%). preferable. It is also possible to partially replace these solvents with low boiling point organic solvents such as tetrahydrofuran, dichloromethane, benzene, toluene, and methanol within a range that does not cause a decrease in conversion rate or yield of the target product.
触媒である水酸化カリウム、水酸化ナトリウムは反応系
に固体のまま加えても良いがメタノール、エタノール、
ＤＭＳＯ，ＤＭＦ、ＨＭＰＡ等の溶媒にあらかじめ溶解
させてから用いても良い。Potassium hydroxide and sodium hydroxide, which are catalysts, can be added to the reaction system as solids, but methanol, ethanol,
It may be used after being dissolved in a solvent such as DMSO, DMF, or HMPA.
固体のまま加える場合は粒径２問以下に粉砕して加える
のがより好ましい。If it is added as a solid, it is more preferable to crush it to a particle size of 2 or less before adding it.
水酸化カリウム又は水酸化ナトリウムの使用量ハ原料の
二！・ロベンゼン類に対して０．０１重量％かそれ以上
用いられるが、使用量が少ないと反応時間が長くなる傾
向にあるので０．３重量％〜１０重量％用いるのが好ま
しい。The amount of potassium hydroxide or sodium hydroxide used is the second raw material! - It is used in an amount of 0.01% by weight or more based on lobenzenes, but if the amount used is small, the reaction time tends to be long, so it is preferable to use 0.3% by weight to 10% by weight.
パラホルムアルデヒドは通常入手可能な工業グレードで
充分である。これも反応系に固体のまま加えられる。そ
の使用量は原料の式（１）のニトロベンゼン類に対して
ＣＨ２Ｒ基の〇−位に２個の置換基がある場合は原料に
対して少なくとも等モルかそれより過剰の量が用いられ
る。又、ＣＩ−（２Ｒ基の〇−位に１個の置換基しか存
在しない場合は少なくとも２倍モルかそれより過剰の量
が用いられる。Generally available industrial grade paraformaldehyde is sufficient. This can also be added to the reaction system as a solid. When there are two substituents at the 0-position of the CH2R group, the amount used is at least equimolar or in excess relative to the starting material, the nitrobenzene of formula (1). Further, when only one substituent is present at the ○-position of the CI-(2R group), an amount of at least 2 times the molar excess or more is used.
反応は０〜６０℃で進行するものであり通常加熱したり
冷却したりする必要はないが発熱反応であるため、場合
によっては冷却して室温（２０℃前後）に保つ方が良い
。The reaction proceeds at a temperature of 0 to 60°C, and there is usually no need to heat or cool it, but since it is an exothermic reaction, it is better to cool it and keep it at room temperature (around 20°C) in some cases.
反応時間は前記記載のように使用した触媒量に依存する
が２０分から４０時間程でよい。反応の初期はバラホル
ムアルデヒド及び触媒が溶媒に完溶しないため殊に充分
な攪拌をする必要塾がある。又、空気（酸素）との接触
はなるべくさげた方がよく窒素シール化で行うとより効
果的である。The reaction time depends on the amount of catalyst used as described above, but may be about 20 minutes to 40 hours. At the beginning of the reaction, sufficient stirring is especially necessary since the formaldehyde and the catalyst are not completely dissolved in the solvent. Also, it is better to reduce contact with air (oxygen) as much as possible, and it is more effective to seal it with nitrogen.
反応の進行状況は薄層クロマトグラフィー、ガスクロマ
トグラフィー、液体クロマトグラフィー等で追跡するこ
とができる。反応を停止したい場合は塩酸、硫酸等を反
応系に加え、中性〜弱酸性にするか、水に注加すること
で目的が達せられる。The progress of the reaction can be monitored by thin layer chromatography, gas chromatography, liquid chromatography, etc. If you want to stop the reaction, you can achieve your goal by adding hydrochloric acid, sulfuric acid, etc. to the reaction system to make it neutral to weakly acidic, or by pouring it into water.
反応液から目的化合物を分離するには公知の方法が適用
出来る。例えば反応液を中性とし、真空蒸留するか、反
応液を水に注加した後、中性″７１１
〜弱酸性とし酢酸エチルのような有機溶剤が抽出する方
法が採用出来る。ただし目的化合物は水に少量溶解する
ため、水で処理を行う場合には飽和食塩水のような塩類
を含む水を用いると良い。Known methods can be applied to separate the target compound from the reaction solution. For example, the reaction solution can be neutralized and vacuum distilled, or the reaction solution can be poured into water and then made neutral to weakly acidic and extracted with an organic solvent such as ethyl acetate.However, the target compound can be extracted by Since it dissolves in a small amount in water, when processing with water, it is recommended to use water containing salts such as saturated saline.
あるが必要なら再結晶又は蒸留を行ったりカラことが出
来る。However, if necessary, it can be recrystallized or distilled.
実施例 実施例により本発明を更に詳細に説明する。Example The present invention will be explained in more detail with reference to Examples.
実施例１゜
反応器に０−ニトロトルエン６４．３ｍｇとＤＭＳＯ２
ｍｌとパラホルムアルデヒド３２４１１１ｇを加え、攪
拌下に粒径Ｑ、５＋ｎｙｎ以下に粉砕した水酸化カリウ
ム１２１ｍｇを入れた。室温下で１時間攪拌した後、反
応液を飽和食塩水ＩＱｍｌに加え５％塩酸で液性を弱酸
性（ｐＨ４〜５）とした後酢酸エチル（１０ｍｌ、３回
）で抽出した。有機層は飽和食塩水１０叫で３回洗浄し
た後、無水芒硝で乾燥した。その後酢酸エチルの大部分
を減圧留去した後シリカゲルカラム（ワコーゲルＣ−２
００）精製し淡黄色液体の’２−（ｏ−ニトロフェニル
）−１，３−フロパンジオール８１０ｍｇ（収率８８％
）を得た。Example 1゜64.3 mg of 0-nitrotoluene and DMSO2 were placed in a reactor.
ml and 324,111 g of paraformaldehyde were added thereto, and 121 mg of potassium hydroxide pulverized to a particle size of Q, 5+nyn or less was added under stirring. After stirring at room temperature for 1 hour, the reaction solution was added to IQml of saturated brine, made weakly acidic (pH 4-5) with 5% hydrochloric acid, and extracted with ethyl acetate (10ml, 3 times). The organic layer was washed three times with 10 portions of saturated saline and then dried with anhydrous sodium sulfate. After that, most of the ethyl acetate was distilled off under reduced pressure, and then a silica gel column (Wakogel C-2
00) 810 mg of purified pale yellow liquid '2-(o-nitrophenyl)-1,3-furopanediol (yield: 88%)
) was obtained.
’Ｈ−ＮＭＴ（（ＣＤ Ｃ１３）
δ３．１５ （ｂｒ、 ｓ、 ２Ｉ−（、ＯＨ）δ３．
４．５〜３．７０ （ｍ、 Ｉ Ｉ−（、Ａｒ −ＣＨ
）δ３．９１ （ｄ、 Ｊ−＝＝６．４Ｈｚ、 ４
Ｈ，ＣＨ２０）δ７．１６〜７．７８ （ｍ、 ４．
Ｈ，Ａｒ−Ｈ）実施例２〜６゜
実施例１とほぼ同様にして第２表に示される条件により
２−（ｏ−ニトロフェニル） −１−、３−フロパンジ
オールヲ得り。'H-NMT((CD C13) δ3.15 (br, s, 2I-(,OH) δ3.
4.5-3.70 (m, I I-(, Ar -CH
) δ3.91 (d, J-==6.4Hz, 4
H, CH20) δ7.16-7.78 (m, 4.
H, Ar-H) Examples 2 to 6 2-(o-nitrophenyl)-1-,3-furopanediol was obtained in substantially the same manner as in Example 1 under the conditions shown in Table 2.
１３一
実施例７゜
反応器に２−クロル−６−二トロトルエン２ｇとＤＭＦ
１０叫とパラホルムアルデヒド０．４６ｇを加え、攪
拌下Ｋ Ｏ，５■以下に粉砕した水酸化カリウム０．６
ｇを加えた。室温で３時間攪拌有機相を合せて、飽和食
塩水２０ ｍｌで３回洗浄した後、無水芒硝で乾燥した
。その後溶媒を留去したところ、黄色結晶として２−（
２−クロル−６−ニトロフェニル）エタノールカ２．３
ｇ（粒数率９８％）得られた。13-Example 7゜2-chloro-6-nitrotoluene 2g and DMF in a reactor
0.6 g of potassium hydroxide was added and 0.46 g of paraformaldehyde was added and pulverized to KO,5 or less under stirring.
g was added. The organic phases were stirred at room temperature for 3 hours, washed three times with 20 ml of saturated brine, and dried over anhydrous sodium sulfate. After that, the solvent was distilled off, and 2-(
2-chloro-6-nitrophenyl)ethanol 2.3
g (particle number ratio 98%) was obtained.
ガスクロマトグラフィー分析によると純度は９６％であ
った。さらにクロロホルムで再結晶を行うと、淡黄色結
晶として２．１ｇ（収率９゜％）目的物が得られた。Purity was 96% according to gas chromatography analysis. Further recrystallization from chloroform gave 2.1 g (9% yield) of the desired product as pale yellow crystals.
ｍｐ６０−６２℃
’、ＴＩ−ＮＭＲ（ＣＪ）Ｃ１３，ＴＭＳ ）δ２．２
（ｂｒ、 ｓ、 ＩＨ９ＯＨ）δ３．２ （ｔ、
Ｊ＝６．５Ｈｚ、 ２Ｈ，Ａｒ−ＣＨ２−）δ３．
９ （ｔ、 Ｊ＝６．５Ｈｚ、 ２Ｈ，−ＣＨ５Ｏ
）δ７．１５〜７．８０ （ｍ、 ３Ｈ，Ａｒ−Ｈ）
実施例８
反応器に、３，４−ジメチルニトロベンゼン５ｇとＤＭ
ＳＯ２０ｍｌを加え、攪拌下に０．５印以下に粉砕した
水酸化カリウム０．６ｇを添加した。mp60-62℃', TI-NMR (CJ) C13, TMS) δ2.2
(br, s, IH9OH)δ3.2 (t,
J=6.5Hz, 2H, Ar-CH2-) δ3.
9 (t, J=6.5Hz, 2H, -CH5O
) δ7.15-7.80 (m, 3H, Ar-H)
Example 8 In a reactor, 5 g of 3,4-dimethylnitrobenzene and DM
20 ml of SO was added, and while stirring, 0.6 g of potassium hydroxide pulverized to below 0.5 mark was added.
室温で５時間攪拌した後、反応液を飽和食塩水１００
ｍｌに注加し、５％ＨＣｔ水溶液で液性を弱酸性（ｐ）
ｉ４〜５）にした後、酢酸エチル３０ｍ１で３回抽出し
た。有機相を合せて飽和食塩水３０ｍ１で３回洗浄した
後、無水芒硝で乾燥した。After stirring at room temperature for 5 hours, the reaction solution was diluted with 100% saturated brine.
ml, and make the liquid slightly acidic (p) with 5% HCt aqueous solution.
After i4-5), extraction was performed three times with 30 ml of ethyl acetate. The organic phases were combined, washed three times with 30 ml of saturated brine, and then dried over anhydrous sodium sulfate.
その後、溶媒を留去したところ、黄色結晶とし”’Ｃ２
−４２−メーｆルー４−ニトロフェニル）−１，３−プ
ロパンジオールが６６ｇ（粒数率９５％）得られた。ガ
スクロマトグラフィー分析によると純度は９５．５％で
あった。さらに酢酸工ｇ（収率８７％）の目的物が得ら
れた。After that, when the solvent was distilled off, yellow crystals were formed.
66 g (particle number ratio 95%) of -42-me-4-nitrophenyl)-1,3-propanediol was obtained. According to gas chromatography analysis, the purity was 95.5%. Furthermore, the desired product of acetic acid (yield: 87%) was obtained.
ｍｐ ； １３６−１３８°Ｃ
’Ｈ−ＮＭＲ（ｃｌ” −Ａｃｅｔｏｎｅ 、 ＴＭＳ
）δ２．５ （ｓ、 ３Ｈ，ＣＩ（３）
δ２．９ （ｂｒ、 ｓ、 ２Ｈ，ＯＨ）δ３３−３．
８（ｍ、 ＩＨ，ＣＨ）
δ３．９ （ｄ、 ４Ｈ，Ｊ＝６Ｈｚ、 ＣＨ２−０）
δ７．５〜８．１５ （ｍ、 ３Ｈ，Ａｒ−Ｈ）につき
それぞれの生成物を得た。mp; 136-138°C'H-NMR (cl"-Acetone, TMS
) δ2.5 (s, 3H, CI(3) δ2.9 (br, s, 2H, OH) δ33-3.
8 (m, IH, CH) δ3.9 (d, 4H, J=6Hz, CH2-0)
Each product was obtained for δ7.5-8.15 (m, 3H, Ar-H).
操作を行って同表に示される生成物を得た。The operations were carried out to obtain the products shown in the same table.
第 ４ 表
発明の効果
入手容易なニトロベンゼン類から、２−にトロフェニル
）エタノール類を、高収率で得る方法が確立された。Table 4 Effects of the Invention A method for obtaining 2-trophenyl)ethanols in high yield from readily available nitrobenzenes has been established.
Claims (1)
ホルムアミド中、水酸化カリウム又は水酸化ナトリウム
の存在下に式（１） ▲数式、化学式、表等があります▼（１） （式（１）においてＸ、Ｙ及びＺはそれぞれ独立に水素
原子、Ｃ＿１＿〜＿４のアルキル基、ニトロ基又はハロ
ゲン原子を、Ｒは水素原子又はメチル基を表す。但し少
なくとも１個のニトロ基がＣＨ＿２Ｒ基に対してＯ−位
又はＰ−位に置換しているものとする。） で示されるニトロベンゼン類とパラホルムアルデヒドを
反応させることを特徴とする式（２） ▲数式、化学式、表等があります▼（２） （式（２）においてＸ、Ｙ、Ｚ及びＲは前記と同じ意味
を、ｎは１又は２をそれぞれ表す。）で示される２−（
ニトロフェニル）又は２−（ニトロフェニル）−２−置
換−エタノール類の製造方法[Claims] 1 In the presence of potassium hydroxide or sodium hydroxide in dimethyl sulfoxide and/or N,N-dimethylformamide, the formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) (Formula In (1), X, Y and Z each independently represent a hydrogen atom, an alkyl group of C_1_-_4, a nitro group or a halogen atom, and R represents a hydrogen atom or a methyl group.However, at least one nitro group is a CH_2R group. Formula (2) characterized by the reaction of nitrobenzene and paraformaldehyde (substituted at O-position or P-position) ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ (2) (In formula (2), X, Y, Z and R have the same meanings as above, and n represents 1 or 2, respectively.) 2-(
Method for producing (nitrophenyl) or 2-(nitrophenyl)-2-substituted ethanols
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62042803A JPS63210289A (en) | 1987-02-27 | 1987-02-27 | Production of 2-(nitrophenyl) or 2-(nitrophenyl)-2-substituted ethanols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62042803A JPS63210289A (en) | 1987-02-27 | 1987-02-27 | Production of 2-(nitrophenyl) or 2-(nitrophenyl)-2-substituted ethanols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63210289A true JPS63210289A (en) | 1988-08-31 |
Family
ID=12646120
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62042803A Pending JPS63210289A (en) | 1987-02-27 | 1987-02-27 | Production of 2-(nitrophenyl) or 2-(nitrophenyl)-2-substituted ethanols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63210289A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5651234A (en) * | 1978-09-25 | 1981-05-08 | Midland Ross Corp | Method of supplying charge into vertical continuous gasifying furnace and its vertical continuous gasifying furnace |
| JPS61270383A (en) * | 1985-05-23 | 1986-11-29 | Nippon Kayaku Co Ltd | Production of 2-(nitrophenyl)-2-substituted-ethanols |
-
1987
- 1987-02-27 JP JP62042803A patent/JPS63210289A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5651234A (en) * | 1978-09-25 | 1981-05-08 | Midland Ross Corp | Method of supplying charge into vertical continuous gasifying furnace and its vertical continuous gasifying furnace |
| JPS61270383A (en) * | 1985-05-23 | 1986-11-29 | Nippon Kayaku Co Ltd | Production of 2-(nitrophenyl)-2-substituted-ethanols |
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