JPH02124837A - 1,4,5,8-tetrakis(halogenomethyl)naphthalene, derivative thereof and preparation thereof - Google Patents

1,4,5,8-tetrakis(halogenomethyl)naphthalene, derivative thereof and preparation thereof

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Publication number
JPH02124837A
JPH02124837A JP27908388A JP27908388A JPH02124837A JP H02124837 A JPH02124837 A JP H02124837A JP 27908388 A JP27908388 A JP 27908388A JP 27908388 A JP27908388 A JP 27908388A JP H02124837 A JPH02124837 A JP H02124837A
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Japan
Prior art keywords
naphthalene
tetrakis
formula
halogenomethyl
reaction
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JP2500316B2 (en
Inventor
Toshihiro Kamata
鎌田　利紘
Yasuo Gama
蒲　康夫
Nobuhide Wasada
和佐田　宣英
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National Institute of Advanced Industrial Science and Technology AIST
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Agency of Industrial Science and Technology
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Abstract

NEW MATERIAL:Compounds of formula I (X is Br or Cl) and formula II (R is isothiuronium chloride [SC(NH2)2]<+>X<->). USE:A monomer for polyesters or polyethers or a raw material for producing surfactants. PREPARATION:1,4,5,8-Tetrakis(hydroxymethyl)naphthalene of formula III is suspended in an inactive organic solvent such as an ether or benzene and subsequently treated with a halogenating agent (e.g., phosphorus tribromide) dropped therein to provide the compound of formula I, which is further treated with thiourea in a solvent such as an alcohol at 50-80 deg.C to provide the compound of formula II.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、新規化合物である１、４．５．８−テトラキ
ズ（ハロゲノメチル）ナフタレン、およびその誘導体、
ならびにこれら化合物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention provides novel compounds, 1,4,5,8-tetrakis(halogenomethyl)naphthalene, and its derivatives,
and methods for producing these compounds.

〔従来技術〕[Prior art]

従来から、ナフタレンのベリ位（ｌ、８位）にハロゲノ
メチル基（−ＣＨ２Ｘ、χはハロゲン原子）が置換した
１、８−ビス（ハロゲノメチル）ナフタレンはよく知ら
れた化合物である。Conventionally, 1,8-bis(halogenomethyl)naphthalene in which a halogenomethyl group (-CH2X, .chi. is a halogen atom) is substituted at the bery position (l, 8-position) of naphthalene is a well-known compound.

〔発明が解決しようとする課題〕[Problem to be solved by the invention]

しかしながら、ナフタレン環の、更に、他のベリ位（４
，５位）にもハロゲノメチル基が置換したビスペリ置換
体の１．４．５．８−テトラキズ（ハロゲノメチル）ナ
フタレンは、応用面での幅広い用途が期待されているに
もかかわらず、合成化学上の困難さから現在に至るまで
未知化合物である。However, the other bery position (4
Although bisperi-substituted 1,4,5,8-tetrakis(halogenomethyl)naphthalene, which is also substituted with a halogenomethyl group (5-position), is expected to have a wide range of applications, it is still difficult to use in synthetic chemistry. Due to the above difficulties, it remains an unknown compound until now.

すなわち本発明は、新規化合物の１．４．５．８−テト
ラキズ（ハロゲノメチル）ナフタレンとその誘導体、お
よびこれら化合物の製造方法を提供することを目的とす
るものである。That is, an object of the present invention is to provide a novel compound of 1,4,5,8-tetrakis(halogenomethyl)naphthalene and its derivatives, and a method for producing these compounds.

〔課題を解決するための手段〕[Means to solve the problem]

上記目的を達成する本発明に係る新規化合物の１．４．
５．８−テトラキズ（ハロゲノメチル）ナフタレンは、
下記一般式（Ｉ）で示される。1.4. New compounds according to the present invention that achieve the above objects.
5.8-Tetrakis(halogenomethyl)naphthalene is
It is represented by the following general formula (I).

ただしく１）式中、Ｘは臭素原子または塩素原子である
。However, in the formula 1), X is a bromine atom or a chlorine atom.

また、本発明に係る新規化合物の１．４．５．ε−テト
ラキズ（ハロゲノメチル）ナフタレンＭ４体は下記−能
代（ｎ）で示される。In addition, 1.4.5. of the new compound according to the present invention. The ε-tetrakis(halogenomethyl)naphthalene M4 is represented by Noshiro (n) below.

ただしくｎ）式中、Ｒはハロゲン化イソチウロニオ基　
−［５Ｃ（ＮＴｏ）　！］”　Ｘ−であり、Ｘは臭素原
子または塩素原子である。(n) In the formula, R is a halogenated isothiuronio group
-[5C(NTo)! ]” X-, and X is a bromine atom or a chlorine atom.

そして上記一般式（Ｉ）で示される１、４．５．８−テ
トラキズ（ハロゲノメチル）ナフタレンは、下記構造式
（Ａ）で示される１、４，５．８−テトラキズ（ヒドロ
キシメチル）ナフタレンにハロゲン化剤を作用させるこ
とにより製造される。The 1,4,5.8-tetrakis(halogenomethyl)naphthalene represented by the above general formula (I) is converted into the 1,4,5,8-tetrakis(hydroxymethyl)naphthalene represented by the following structural formula (A). Manufactured by applying a halogenating agent.

また−能代（１）において、Ｘが塩素原子の、下記構造
式（Ｃ）で示される１、４，５．８−テトラキズ（クロ
ロメチル）ナフタレンは、上記のように１．４．５．８
−テトラキズ（ヒドロキシメチル）ナフタレン（Ａ）と
ハロゲン化剤との反応によって製造される以外に、下記
構造式（Ｂ）で示される１、４．５．８−テトラキズ（
ブロモメチル）ナフタレンをハロゲン交換剤で処理する
ハロゲン交換反応を利用しても製造することができる。- In Noshiro (1), 1,4,5.8-tetrakiz(chloromethyl)naphthalene represented by the following structural formula (C) in which X is a chlorine atom is 1.4.5.8 as described above.
In addition to being produced by the reaction of -tetrakid (hydroxymethyl)naphthalene (A) and a halogenating agent, 1,4,5,8-tetrakid (
It can also be produced using a halogen exchange reaction in which bromomethyl)naphthalene is treated with a halogen exchange agent.

また、上記−能代（ＩＩ）で示される１、４，５．８−
テトラキズ（ハロゲノメチル）ナフタレン誘導体は、上
記構造式（１）で示される１、４．５．８−テトラキズ
（ハロゲノメチル）ナフタレンをチオ尿素で処理するこ
とにより製造される。In addition, 1, 4, 5.8- shown in the above - Noshiro (II)
Tetrakis(halogenomethyl)naphthalene derivatives are produced by treating 1,4,5,8-tetrakis(halogenomethyl)naphthalene represented by the above structural formula (1) with thiourea.

本発明の１．４．５．８−テトラキズ（ハロゲノメチル
）ナフタレン（１）の製造方法によれば、反応はエーテ
ル類やベンゼンなどの不活性有機溶媒中で行われる。先
ず、原料の１．４．５．８−テトラキズ（ヒドロキシメ
チル）ナフタレン（Ａ）に上記不活性有機溶媒を加えて
懸濁液をつくり、次に、これにハロゲン化剤を滴下して
ハロゲン化反応を行う。ハロゲン化剤としては、三臭化
リンなどのハロゲン化リンや塩化チオニルなどのハロゲ
ン化チオニルなどが用いられる０通常、ハロゲン化剤は
約５倍量と過剰に使用し、これを数回に分けて添加して
ハロゲン化反応を完結させるようにする０反応温度は室
温ないし５０℃の範囲であり、また、反応収率を上げる
ために、反応中たえず効率よく攪拌することが好ましい
。According to the method for producing 1.4.5.8-tetrakis(halogenomethyl)naphthalene (1) of the present invention, the reaction is carried out in an inert organic solvent such as ethers or benzene. First, the above-mentioned inert organic solvent is added to the raw material 1.4.5.8-tetrakiz(hydroxymethyl)naphthalene (A) to create a suspension, and then a halogenating agent is added dropwise to the suspension for halogenation. Perform the reaction. As the halogenating agent, phosphorus halides such as phosphorus tribromide and thionyl halides such as thionyl chloride are used.Normally, the halogenating agent is used in excess of about 5 times the amount and divided into several doses. The reaction temperature at which the halogenation reaction is completed by addition is in the range of room temperature to 50°C, and in order to increase the reaction yield, it is preferable to constantly stir efficiently during the reaction.

このようにして反応を行うと、ハロゲン化反応の進行と
ともに、原料の１．４，５．８−テトラキズ（ヒドロキ
シメチル）ナフタレン（Ａ）の懸濁液はすみやかに消え
て透明な溶液となり、間もなく生成物の１．４．５．８
−テトラキズ（ハロゲノメチル）ナフタレン（１）が白
色沈澱物として反応液から分離してくる０反応終了後に
、この沈澱物を濾過・捕集すれば、１．４．５．８−テ
トラキズ（ハロゲノメチル）ナフタレン（Ｉ）を得るこ
とができる。When the reaction is carried out in this way, as the halogenation reaction progresses, the suspension of the raw material 1,4,5,8-tetrakiz(hydroxymethyl)naphthalene (A) quickly disappears and becomes a transparent solution, and soon 1.4.5.8 of the product
-Tetra-wound (halogenomethyl)naphthalene (1) separates from the reaction solution as a white precipitate.After the reaction is complete, if this precipitate is filtered and collected, 1.4.5.8-tetra-wound (halogenomethyl) ) Naphthalene (I) can be obtained.

（Ａ） ただしくＩ）式中、Ｘは臭素原子または塩素原子である
。(A) Wherein I), X is a bromine atom or a chlorine atom.

なお、１．４．５．８−テトラキズ（ハロゲノメチル）
ナフタレン（Ｉ）の製造の原料となる１、４゜５．８−
テトラキズ（ヒドロキシメチル）ナフタレン（Ａ）は、
下記反応式に示すように、通常重版されているナフタレ
ン−１，４，５，８−テトラカルボン酸（Ｄ）をアルカ
リ溶液中で硫酸ジメチルで処理してナフタレン−１，４
，５，８−テトラカルボン酸テトラメチルエステル（Ｅ
）としたのち、水素化剤で還元して、そのエステル基（
−ＣＯ！Ｍｅ）をヒドロキシメチル基（−ＣＯ，ＯＨ）
に変換することによって製造される。In addition, 1.4.5.8-tetra scratch (halogenomethyl)
1,4゜5.8- which is the raw material for the production of naphthalene (I)
Tetra-wound (hydroxymethyl) naphthalene (A) is
As shown in the reaction formula below, naphthalene-1,4,5,8-tetracarboxylic acid (D), which is usually reprinted, is treated with dimethyl sulfate in an alkaline solution to form naphthalene-1,4.
,5,8-tetracarboxylic acid tetramethyl ester (E
), and then reduced with a hydrogenating agent to form the ester group (
-CO! Me) to a hydroxymethyl group (-CO,OH)
Manufactured by converting into

（Ｄ） （Ｅ） （Ａ） また、本発明によれば、１，４．５．８−テトラキズ（
ハロゲノメチル）ナフタレン（１）においてＸが塩素原
子の場合の製造方法として、上記の１．４．５．８−テ
トラキズ（ヒドロキシメチル）ナフタレン（Ａ）を原料
とする製造方法のほかに、更に、ハロゲン交換反応を用
いる製造方法が提供される。すなわち、１．４．５．８
−テトラキズ（ブロモメチル）ナフタレン（Ｂ）に塩化
リチウムをハロゲン交換剤として作用させると、下記反
応式に示すようにハロゲン交換反応が起こり、原料分子
中の４個のブロム原子が塩素原子に置換された１、４．
５．　８−テトラキズ（クロロメチル）ナフタレン（Ｃ
）が得られる。(D) (E) (A) Further, according to the present invention, 1,4.5.8-tetra scratch (
In addition to the production method using the above-mentioned 1.4.5.8-tetrakiz(hydroxymethyl)naphthalene (A) as a raw material, as a production method when X is a chlorine atom in halogenomethyl)naphthalene (1), A manufacturing method using a halogen exchange reaction is provided. That is, 1.4.5.8
- When lithium chloride acts as a halogen exchange agent on tetrakid(bromomethyl)naphthalene (B), a halogen exchange reaction occurs as shown in the reaction formula below, and four bromine atoms in the raw material molecule are replaced with chlorine atoms. 1, 4.
5. 8-Tetrakid(chloromethyl)naphthalene(C
) is obtained.

（Ｂ） （Ｃ） 反応は、アセトンやジメチルホルムアミドなどを溶媒と
して用いて行われ、反応温度は室温ないし５０℃の範囲
であり、また、反応時間は１０ないし２０時間で十分で
ある。このようにして反応を行うと、反応の進行ととも
に原料の臭化物（Ｂ）４は溶けて透明な溶液となるので
、反応終了後に水で処理すると生成物の１．４．５．８
−テトラキズ（クロロメチル）ナフタレン（Ｃ）が得ら
れる。(B) (C) The reaction is carried out using acetone, dimethylformamide, etc. as a solvent, the reaction temperature is in the range of room temperature to 50°C, and the reaction time is sufficient for 10 to 20 hours. When the reaction is carried out in this way, as the reaction progresses, the raw material bromide (B) 4 dissolves and becomes a transparent solution, so if it is treated with water after the reaction, the product 1.4.5.8
-Tetrakid(chloromethyl)naphthalene (C) is obtained.

次に、このようにして得られた１、４．５．８−テトラ
キズ（ハロゲノメチル）ナフタレン（１）をチオ尿素で
処理すると、１，４．５．８−テトラキズ（ハロゲノメ
チル）ナフタレン（１）のチオ尿素誘導体である１、４
．５．８−テトラキズ（イソチウロニオメチル）ナフタ
レン−テトラハライド（ｎ）を得ることができる。反応
はアルコールなどの溶媒中で行われ、その反応温度は５
０℃ないし８０℃の範囲である０反応の進行とともに、
原料である１、４，５．８−テトラキズ（ハロゲノメチ
ル）ナフタレン（１）とチオ尿素の結晶は消え、新しく
、下記反応式で示すように新規化合物１，４，５．８−
テトラキズ（イソチウロニオメチル）ナフタレン−テト
ラハライド（ｎ）の結晶が得られる。Next, when the thus obtained 1,4,5.8-tetrakis(halogenomethyl)naphthalene (1) is treated with thiourea, 1,4,5,8-tetrakis(halogenomethyl)naphthalene (1) is treated with thiourea. ) are thiourea derivatives 1, 4
．． 5.8-tetrakiz(isothiuroniomethyl)naphthalene-tetrahalide (n) can be obtained. The reaction is carried out in a solvent such as alcohol, and the reaction temperature is 5
With the progress of the 0 reaction, which ranges from 0°C to 80°C,
The raw materials 1,4,5.8-tetrakis(halogenomethyl)naphthalene (1) and thiourea crystals disappeared, and a new compound 1,4,5.8- was formed as shown in the reaction formula below.
Crystals of tetra-wound (isothiuroniomethyl) naphthalene-tetrahalide (n) are obtained.

（１）　　　　　　　　　　　　　　　　（ｎ）ただし
く１）式中、Ｘは臭素原子または塩素原子であり、（ｆ
ｆ）式中、Ｒはハロゲン化イソチウロニオ基（−［５Ｃ
（Ｎｌ２）　Ｚ］”　Ｘ−）である。(1) (n) Provided that 1) In the formula, X is a bromine atom or a chlorine atom, and (f
f) In the formula, R is a halogenated isothiuronio group (-[5C
(Nl2)Z]"X-).

本発明で得られた１、４．５．８−テトラキズ（ハロゲ
ノメチル）ナフタレン（１）およびそのチオ尿素誘導体
であるＬ４，５．８−テトラキズ（イソチウロニオメチ
ル）ナフタレン−テトラハライド（ＩＩ）は、いずれも
新規化合物である。1,4,5,8-tetrakis(halogenomethyl)naphthalene (1) obtained in the present invention and its thiourea derivative L4,5,8-tetrakis(isothiuroniomethyl)naphthalene-tetrahalide (II) are all new compounds.

以下、本発明を実施例により、さらに詳述する。Hereinafter, the present invention will be explained in more detail with reference to Examples.

〔実施例〕〔Example〕

参考例１ ナフタレン−１，４，５，８−テトラカルボン酸テトラ
メチルエステル（Ｅ）の製造。Reference Example 1 Production of naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E).

炭酸ナトリウムＬ６ｇを水２００　ｍｌに溶かした溶液
にナフタレン−１，４，５，８−テトラカルボン酸（Ｄ
）１５．２ｇを少しずつ添加した。カルボン酸が反応す
るにつれ炭酸ガスの気泡が激しく発生した。１．５時間
かけてカルボン酸を添加した後、反応液を約４０℃の水
浴で３０分加熱してカルボン酸の結晶を完全に溶かした
。この溶液に硫酸ジメチル１９ｗ１を５分で滴下し、混
合物を５０℃で４０分反応させた。Naphthalene-1,4,5,8-tetracarboxylic acid (D
) was added little by little. As the carboxylic acid reacted, carbon dioxide gas bubbles were generated violently. After adding the carboxylic acid over 1.5 hours, the reaction solution was heated in a water bath at about 40° C. for 30 minutes to completely dissolve the carboxylic acid crystals. Dimethyl sulfate 19w1 was added dropwise to this solution over 5 minutes, and the mixture was reacted at 50° C. for 40 minutes.

次に、炭酸ナトリウムｌ１ｇ　、続いて硫酸ジメチル１
９／を添加して４０分同温度で反応させた後、更に、炭
酸ナトリウム５．５ｇと硫酸ジメチル１〇−を順次加え
、１時間攪拌して反応を終了させた。反応混合物を室温
に下げ、析出した白色沈澱物を吸引濾過し水洗して乾燥
した。このようにして得たものを、ジオキサンより再結
晶して精製すると、ナフタレン−１，４，５，８−テト
ラカルボン酸テトラメチルエステル（Ｅ）が無色結晶と
して得られた（１５．０ｇ、収率８４％）。Then 1 g of sodium carbonate followed by 1 g of dimethyl sulfate
After adding 9/- and reacting at the same temperature for 40 minutes, 5.5 g of sodium carbonate and 10-dimethyl sulfate were successively added and stirred for 1 hour to complete the reaction. The reaction mixture was cooled to room temperature, and the precipitated white precipitate was suction filtered, washed with water, and dried. The product thus obtained was purified by recrystallization from dioxane, and naphthalene-1,4,5,8-tetracarboxylic acid tetramethyl ester (E) was obtained as colorless crystals (15.0 g, yield rate 84%).

ｍ、ｐ、　１９８−１９９℃。m, p, 198-199°C.

元素分析：測定値Ｃ：６０．２１．　Ｈ；４．５０計算
値Ｃ；６０．００．　Ｈ；４．４８（Ｃ＋ｓＨ＋６０ｇ
）高分解能質量分析：測定値３６０．０７８（計算値３
６０．０８５）参考例２ １．４，５．８−テトラキズ（ヒドロキシメチル）ナフ
タレン（Ａ）の製造。Elemental analysis: Measured value C: 60.21. H; 4.50 Calculated value C; 60.00. H; 4.48 (C+sH+60g
) High-resolution mass spectrometry: Measured value 360.078 (calculated value 3
60.085) Reference Example 2 Production of 1.4,5.8-tetrakis(hydroxymethyl)naphthalene (A).

水素化ジイソブチルアルミニウム１モルを含むヘキサン
１０００−の攪拌溶液に、ナフタレン−１，４，５，８
−テトラカルボン酸テトラメチルエスチル（Ｅ）２５ｇ
の結晶を少しずつ添加した。1,4,5,8 naphthalene in a stirred solution of 1,000 ml of hexane containing 1 mole of diisobutylaluminum hydride.
-25 g of tetramethyl ethyl tetracarboxylate (E)
The crystals were added little by little.

発熱により反応液が室温を越えないように、時々反応フ
ラスコを氷水浴で冷却した。エステルは添加と共にすみ
やかに溶解し透明な反応液が得られた。添加終了後、反
応液を更に８日間室温で攪拌した０反応混合物に、冷却
下、メタノール、水、希塩酸の順で添加して過剰の水素
化物を分解し、更に水を加えて室温で攪拌した。The reaction flask was occasionally cooled in an ice-water bath to prevent the reaction solution from exceeding room temperature due to exotherm. The ester dissolved immediately upon addition, and a transparent reaction solution was obtained. After the addition was completed, the reaction mixture was further stirred at room temperature for 8 days. To the reaction mixture, methanol, water, and dilute hydrochloric acid were sequentially added under cooling to decompose the excess hydride, and water was further added and stirred at room temperature. .

生じた白色固体を吸引濾過して集め、充分水洗して乾燥
後、ジメチルスルホキシド−クロロホルムの混合溶媒か
ら再結晶すると、１．４．５．８−テトラキズ　（ヒド
ロキシメチル）ナフタレン（Ａ）が無色微結晶として得
られた（１６．２ｇ、収率９４％）。The resulting white solid was collected by suction filtration, thoroughly washed with water, dried, and then recrystallized from a mixed solvent of dimethyl sulfoxide and chloroform. Obtained as crystals (16.2 g, yield 94%).

ｍ、ｐ、２２９−２３１’！＝。m, p, 229-231'! =.

元素分析：測定値Ｃ；６７．８５．　Ｈ；６．３８計算
値Ｃ；６７．７３．　Ｈ；６．５０（Ｃ＋ｔＨ＋ａＯ＊
）高分解能質量分析：測定値２４８．０９６（計算値２
４８．１０５）実施例１ １．４．５．８−テトラキズ（ヒドロキシメチル）ナフ
タレン（Ａ）４２．５ｇを含むジオキサン１．４１１の
懸濁液に、三臭化リン１８０ｍＺを１０分かけて滴下し
た。原料のテトラオールの結晶は間もなく溶解し、新た
に白色固体が析出した。１時間後に、更に三臭化リン１
８０−を加えて１晩攪拌した。氷水浴で冷却下、反応混
合物に水を加えて未反応の三臭化リンを分解した後、更
に水を加えて全体の容量を約３１として、室温で３０分
間攪拌した。析出した白色固体を吸引濾別し、水洗して
乾燥した。このようにして得たものをジオキサンから再
結晶して精製すると、１．４．５．８−テトラキズ（ブ
ロモメチル）ナフタレン（Ｂ）が無色結晶として得られ
た（７９．１ｇ、収率９３％）。Elemental analysis: Measured value C; 67.85. H; 6.38 Calculated value C; 67.73. H; 6.50 (C+tH+aO*
) High-resolution mass spectrometry: Measured value 248.096 (calculated value 2
48.105) Example 1 180 mZ of phosphorus tribromide was added dropwise over 10 minutes to a suspension of 1.411 dioxane containing 42.5 g of 1.4.5.8-tetrakiz(hydroxymethyl)naphthalene (A). did. The raw material tetraol crystals soon dissolved, and a new white solid precipitated. After 1 hour, add 1 more phosphorus tribromide
80- was added and stirred overnight. While cooling in an ice-water bath, water was added to the reaction mixture to decompose unreacted phosphorus tribromide, and then water was further added to bring the total volume to about 31 kg, followed by stirring at room temperature for 30 minutes. The precipitated white solid was filtered off with suction, washed with water and dried. When the product thus obtained was purified by recrystallization from dioxane, 1.4.5.8-tetrakiz(bromomethyl)naphthalene (B) was obtained as colorless crystals (79.1 g, yield 93%). .

繻、ｐ、＞２２０℃（分解） 元素分析：測定値Ｃ；３３．８０．　Ｈ：２．５１計算
値Ｃ３３３，６３，Ｈ；２．４２（ＣｔａＨｔｔＢｒＪ
高分解能質量分析：測定値４９９．７６９質量分析；測
定値５００ １ｆＪ！：（ＩＩ　５００（Ｃ＋４Ｈ＋ｚＢｒｚ　Ｂｒ
ｔ　）ＩＲ（Ｎｕｊｏｌ）　：　ｖ　＝５４５ｃｍ−’
　（Ｃ−Ｂｒ）実施例２ ジメチルホルムアミド１５−に塩化リチウム０．３ｇを
溶かした溶液に、１．４．５．８−テトラキズ（ブロモ
メチル）ナフタレン（Ｂ）０．３ｇを加えて室温で攪拌
した。テトラブロマイドの白色固体は反応の進行ととも
に次第に溶け、１時間後には透明な溶液に変化した。１
晩室温で攪拌後、水を加えて全体を５００−として、室
温で１時間攪拌した。生じた沈澱物を集め、水洗して乾
燥すると、無色固体の１．４．５．８−テトラキズ（ク
ロロメチル）ナフタレン（Ｃ）が得られた。このように
して得たものを、更に、ジメチルスルホキシド−メタノ
ール−水系の混合溶媒から再結晶して精製した（０．１
８７ｇ、収率９７％）。Satin, p, >220°C (decomposition) Elemental analysis: Measured value C; 33.80. H: 2.51 Calculated value C333,63,H; 2.42 (CtaHttBrJ
High-resolution mass spectrometry: Measured value 499.769 mass spectrometry; Measured value 500 1fJ! :(II 500(C+4H+zBrz Br
t) IR (Nujol): v = 545 cm-'
(C-Br) Example 2 To a solution of 0.3 g of lithium chloride dissolved in dimethylformamide 15-, 0.3 g of 1.4.5.8-tetrakis(bromomethyl)naphthalene (B) was added and stirred at room temperature. . The white solid of tetrabromide gradually dissolved as the reaction progressed and turned into a clear solution after 1 hour. 1
After stirring at room temperature overnight, water was added to make the whole mixture 500-, and the mixture was stirred at room temperature for 1 hour. The resulting precipitate was collected, washed with water, and dried to obtain 1.4.5.8-tetrakis(chloromethyl)naphthalene (C) as a colorless solid. The product thus obtained was further purified by recrystallization from a dimethyl sulfoxide-methanol-water mixed solvent (0.1
87 g, yield 97%).

ｍ、ｐ、２０７−２０９℃。m, p, 207-209°C.

元素分析：測定値Ｃ；５２．３５．　Ｈ：３．５１計算
値Ｃ；５２．２０．　Ｈ：３．７６（Ｃ＋４Ｈ＋ｚＣ１
＊）質量分析：測定値３２２ ’Ｈ−ＮＭＲ（ＤＭＳＯ−ｄａ）：δ＝７．８２（ｓ、
４Ｈ，ＡｒＨ）５．３９（ｓ、８８°、ｃＨｚ） ＩＲ（Ｎｕｊｏｌ）　：　Ｖ　＝６２０ｃｍ−’　（Ｃ
−ＣＩ）実施例３ チオ尿素６．０８ｇを含む９９％エタノール２００ｍの
加熱・攪拌溶液に、１，４，５．８−テトラキズ（ブロ
モメチル）ナフタレン（Ｂ　ＨＯｇの結晶を少しずつ添
加した。発熱とともに臭化物の結晶は速やかに溶け、新
たに白色固体が析出した。Elemental analysis: Measured value C; 52.35. H: 3.51 Calculated value C; 52.20. H:3.76(C+4H+zC1
*) Mass spectrometry: Measured value 322'H-NMR (DMSO-da): δ = 7.82 (s,
4H, ArH) 5.39 (s, 88°, cHz) IR (Nujol): V = 620 cm-' (C
-CI) Example 3 Crystals of 1,4,5.8-tetrakis(bromomethyl)naphthalene (B HOg) were added little by little to a heated and stirred solution of 200 m of 99% ethanol containing 6.08 g of thiourea. The bromide crystals quickly dissolved and a new white solid precipitated.

この白色懸濁液を、更に２時間攪拌しながら加熱・還流
して反応を終結させた。反応混合物にベンゼン１００−
を加えて氷冷却下３０分攪拌した後、生成物を吸引濾過
して集めた。このようにして得たものを、ベンゼンで２
回、次いでペンタンで２回洗浄した後真空乾燥すると、
１．４．５゜８−テトラキズ（ブロモメチル）ナフタレ
ンの千オ尿素誘導体である１、４．５．８−テトラキズ
（イソチウロニオメチル）ナフタレン−テトラブロマイ
ド（ＩＩ）が白色粉末状結晶として得られた（１５．６
１ｇ、収率９７％）。This white suspension was further heated and refluxed while stirring for 2 hours to terminate the reaction. Benzene 100-
After stirring for 30 minutes under ice cooling, the product was collected by suction filtration. The product obtained in this way is diluted with benzene.
After washing twice with pentane and then drying under vacuum,
1,4.5° 1,4.5.8-Tetrakis(isothiuroniomethyl)naphthalene-tetrabromide (II), which is a 1,000-urea derivative of 8-tetrakis(bromomethyl)naphthalene, was obtained as white powdery crystals. (15.6
1 g, yield 97%).

階、ｐ、＞１９５℃（分解） 元素分析：測定値Ｃ；２６．５９．　Ｈ；３．８０計算
値Ｃ；２６．８７．　Ｈ：３．５１（Ｃ＋８ＨｚｓＮｓ
ＳＪｒ４’Ｈ−ＮＭＲ（ＤＭＳＯ−ｄｉ）　：δ＝９．
２２（ｓ、１６Ｈ，Ｃ（ＮＯｘ）ｔＢｒ）７．８３（ｓ
、４Ｈ，ＡｒＨ） ５．１６（ｓ、８Ｈ，ＣＨｌ） 実施例４ チオ尿素４．７２ｇを含む９９％エタノール１５０ｗ１
の加熱・攪拌溶液に、１，４．５．８−テトラキズ（ク
ロロメチル）ナフタレン（Ｃ）５．０ｇの結晶を少しず
つ添加した。塩化物の結晶は速やかに溶け、新たに白色
固体が析出した。この白色懸濁液を、更に２時間攪拌し
ながら加熱・還流して反応を終結させた０反応部合物に
ベンゼン７０−を加えて氷冷下３０分攪拌した後、生成
物を吸引濾過して集めた。このようにして得たものを、
ベンゼンで３回、次いでペンタンで２回洗浄した後真空
乾燥すると、１．４，５．８−テトラキズ（クロロメチ
ル）ナフタレンのチオ尿素誘導体である１、４，５．８
−テトラキズ（イソチウロニオメチル）ナフタレン−テ
トラクロライド（ｎ）が白色粉末状結晶として得られた
（９．２３ｇ、収率９５％）。Floor, p, >195°C (decomposition) Elemental analysis: Measured value C; 26.59. H: 3.80 Calculated value C: 26.87. H: 3.51 (C+8HzsNs
SJr4'H-NMR (DMSO-di): δ=9.
22(s, 16H, C(NOx)tBr)7.83(s
, 4H, ArH) 5.16 (s, 8H, CHl) Example 4 99% ethanol 150 w1 containing 4.72 g of thiourea
5.0 g of crystals of 1,4.5.8-tetrakiz(chloromethyl)naphthalene (C) were added little by little to the heated and stirred solution. The chloride crystals quickly dissolved and a new white solid precipitated. This white suspension was further heated and refluxed with stirring for 2 hours to complete the reaction. Benzene 70- was added to the 0 reaction mixture and stirred for 30 minutes under ice cooling, and the product was suction filtered. I collected them. What you get in this way,
After washing three times with benzene and then twice with pentane and drying in vacuum, 1,4,5.8, a thiourea derivative of 1,4,5,8-tetrakid(chloromethyl)naphthalene, was obtained.
-tetrakiz(isothiuroniomethyl)naphthalene-tetrachloride (n) was obtained as white powdery crystals (9.23 g, yield 95%).

ｍ、ｐ、　＞１８０℃（分解） 元素分析：測定値Ｃ；３４．８７．　Ｈ；４．３５計算
値Ｃ；３４．５０．　Ｈ；４．５０（Ｃ＋５ＨｚｓＮｓ
Ｓ４Ｃ１ａ）’Ｈ−ＮＭＲ（ＤＭＳＯ−ｄ６）　：δ＝
９．２５（ｓ、　１６８．Ｃ（ＮＨり　２Ｃ１）７．８
１　（ｓ、　４Ｈ，ＡｒＨ） ５．１４（ｓ、８Ｈ，ｃＨｚ） 〔発明の効果〕 以上述べたように本発明によれば、新規化合物として、
１．４，５．８−テトラキズ（ハロゲノメチル）ナフタ
レンおよびそのチオ尿素誘導体の１．４，５．８−テト
ラキズ（インチウロニオメチル）ナフタレン−テトラハ
ライドが得られる。m, p, >180°C (decomposition) Elemental analysis: Measured value C; 34.87. H; 4.35 Calculated value C; 34.50. H; 4.50 (C+5HzsNs
S4C1a)'H-NMR (DMSO-d6): δ=
9.25 (s, 168.C (NHri 2C1) 7.8
1 (s, 4H, ArH) 5.14 (s, 8H, cHz) [Effects of the invention] As described above, according to the present invention, as a new compound,
1,4,5,8-tetrakis(inthiuroniomethyl)naphthalene-tetrahalides of 1,4,5,8-tetrakis(halogenomethyl)naphthalene and its thiourea derivatives are obtained.

かかる化合物は、ポリエステルやポリエーテル用モノマ
ーとして有用であり、また界面活性剤製造原料としても
有用である。Such compounds are useful as monomers for polyesters and polyethers, and are also useful as raw materials for producing surfactants.

かつ、かかる化合物は、市販のナフタレン−１，４，５
，８−テトラカルボン酸から容易に製造することができ
る。and such compound is commercially available naphthalene-1,4,5
, 8-tetracarboxylic acid.

ＶV

Claims (1)

【特許請求の範囲】 １、下記一般式（ I ）で示される１，４，５，８−テ
トラキズ（ハロゲノメチル）ナフタレン。 ▲数式、化学式、表等があります▼（ I ） ただし（ I ）式中、Ｘは臭素原子または塩 素原子である。 ２、下記一般式（II）で示される１，４，５，８−テト
ラキズ（ハロゲノメチル）ナフタレン誘導体。 ▲数式、化学式、表等があります▼（II） ただし（II）式中、Ｒはハロゲン化イソチ ウロニオ基−［ＳＣ（ＮＨ＿２）＿２］＾＋Ｘ＾−であ
り、Ｘは臭素原子または塩素原子である。 ３、下記構造式（Ａ）で示される１，４，５，８−テト
ラキズ（ヒドロキシメチル）ナフタレンをハロゲン化剤
で処理することを特徴とする下記一般式（ I ）で示さ
れる１，４，５，８−テトラキズ（ハロゲノメチル）ナ
フタレンの製造方法。 ▲数式、化学式、表等があります▼（Ａ） ただし（ I ）式中、Ｘは臭素原子または塩 素原子である。 ４、下記構造式（Ｂ）で示される１，４，５，８−テト
ラキズ（ブロモメチル）ナフタレンをハロゲン交換剤で
処理することを特徴とする下記構造式（Ｃ）で示される
１，４，５，８−テトラキズ（クロロメチル）ナフタレ
ンの製造方法。 ▲数式、化学式、表等があります▼（Ｂ） ▲数式、化学式、表等があります▼（Ｃ） ５、下記一般式（ I ）で示される１，４，５，８−テ
トラキズ（ハロゲノメチル）ナフタレンをチオ尿素で処
理することを特徴とする下記一般式（II）で示される１
，４，５，８−テトラキズ（ハロゲノメチル）ナフタレ
ン誘導体の製造方法。 ▲数式、化学式、表等があります▼（ I ） ▲数式、化学式、表等があります▼（II） ただし（ I ）式中、Ｘは臭素原子または塩素原子であ
り、（II）式中、Ｒはハロゲン化イソチウロニオ基−［
ＳＣ（ＮＨ＿２）＿２］＾＋Ｘ＾−である。[Claims] 1. 1,4,5,8-tetrakis(halogenomethyl)naphthalene represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) However, in the formula (I), X is a bromine atom or a chlorine atom. 2. 1,4,5,8-tetrakis(halogenomethyl)naphthalene derivative represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) However, in formula (II), R is a halogenated isothiuronio group -[SC(NH_2)_2]^+X^-, and X is a bromine atom or a chlorine atom. . 3. 1,4,5,8-tetrakis(hydroxymethyl)naphthalene represented by the following structural formula (A) is treated with a halogenating agent. A method for producing 5,8-tetra-wound (halogenomethyl)naphthalene. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (A) However, (I) In the formula, X is a bromine atom or a chlorine atom. 4. 1,4,5,5, represented by the following structural formula (C), which is characterized by treating 1,4,5,8-tetrakis(bromomethyl)naphthalene represented by the following structural formula (B) with a halogen exchange agent. , 8-Tetrakidz(chloromethyl)naphthalene manufacturing method. ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (C) 5. 1,4,5,8-tetrakis (halogenomethyl) shown by the general formula (I) below 1 represented by the following general formula (II), characterized by treating naphthalene with thiourea
, 4,5,8-tetrakis(halogenomethyl)naphthalene derivative. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) However, in the formula (I), X is a bromine atom or a chlorine atom, and in the formula (II), R is a halogenated isothiuronio group -[
SC(NH_2)_2]^+X^-.
JP63279083A 1988-11-04 1988-11-04 1,4,5,8-Tetrakis (halogenomethyl) naphthalene derivative and method for producing the same Expired - Lifetime JP2500316B2 (en)

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Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF ORGANIC CHEMISTRY=1982 *

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