JPS625410B2 - - Google Patents
Info
- Publication number
- JPS625410B2 JPS625410B2 JP21412982A JP21412982A JPS625410B2 JP S625410 B2 JPS625410 B2 JP S625410B2 JP 21412982 A JP21412982 A JP 21412982A JP 21412982 A JP21412982 A JP 21412982A JP S625410 B2 JPS625410 B2 JP S625410B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- cyclic
- formula
- phenol
- formaldehyde
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 12
- -1 phenol formaldehyde compound Chemical class 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 150000002989 phenols Chemical class 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 238000005377 adsorption chromatography Methods 0.000 description 4
- 238000010575 fractional recrystallization Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920002866 paraformaldehyde Polymers 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- DDZACMDGXVXOOH-UHFFFAOYSA-N 4-(4-methylphenyl)phenol Chemical group C1=CC(C)=CC=C1C1=CC=C(O)C=C1 DDZACMDGXVXOOH-UHFFFAOYSA-N 0.000 description 1
- JDCUQPSPITUXGL-UHFFFAOYSA-N 4-(4-octylphenyl)phenol Chemical group C1=CC(CCCCCCCC)=CC=C1C1=CC=C(O)C=C1 JDCUQPSPITUXGL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- OQNGCCWBHLEQFN-UHFFFAOYSA-N chloroform;hexane Chemical compound ClC(Cl)Cl.CCCCCC OQNGCCWBHLEQFN-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規な７環状体フエノール・ホルムア
ルデヒド化合物及びその製造法に関するもので、
さらに詳しくは耐熱性に優れた重金属イオンの選
択性吸着剤として有効な７環状体フエノール・ホ
ルムアルデヒド化合物及びその製造法に関する。
従来から各種の廃水中に含まれる銅、水銀、ニ
ツケルなどの重金属イオンの吸着剤としては活性
炭、けいそう土、各種イオン交換樹脂、あるいは
キレート能を有する樹脂たとえば各種クラウンエ
ーテル化合物などが挙げられる。しかしこれらの
うち活性炭、けいそう土、イオン交換樹脂は重金
属イオンに対する選択性に劣りまたクラウンエー
テル化合物は選択性はある程度あるものの、耐熱
性に劣り、かつ高価であり汎用性にも乏しいとい
う欠点があつた。
本発明は重金属イオンに対して極めて優れた選
択吸着能を有し、安価でかつ高耐熱性を有する新
規な７環状体フエノール・ホルムアルデヒド樹脂
を提供するものである。
すなわち本発明は一般式
〔式中ＲはCnH2n＋１（ｎ＝０〜10の整数）で
ある。〕
で表わされる７環状体フエノール・ホルムアルデ
ヒド樹脂類を提供するものである。前記一般式で
表わされる樹脂の特徴はバラ位に特定の基が置換
したフエノール７分子が７個のメチレン基を介し
て水酸基を内側に向けた形で環状体となつている
点でありほぼ環状に配置された水酸基が重金属イ
オンに配位し選択的補促性を示すものである。ま
たこの化合物は耐熱性を有し、安価に製造でき
る。
式中のＲは水素、メチル基、エチル基、プロピ
ル基、ブチル基、オクチル基等の炭素数０〜10の
水素又はアルキル基である。Ｒが炭素数11以上の
アルキル基では環状体が生成せずしたがつて重金
属イオンに対する選択吸着性は発揮されない。
次に本発明の新規化合物の一般的製法を記載す
る。
まずフエノール類１モルに対しホルムアルデヒ
ド類を1.2〜3.0モル配合しこれにフエノール類に
対して２〜４重量倍の非水系溶媒を加えて懸濁さ
せ、ついでアルカリ金属の水酸化物をフエノール
類に対して0.05〜0.5モル％を好ましくは前記溶
剤量の0.5〜2.0％の水に溶解して添加し反応温度
100〜120℃で30〜100時間反応させる。
フエノール類としては構造式
The present invention relates to a novel heptacyclic phenol formaldehyde compound and a method for producing the same.
More specifically, the present invention relates to a heptacyclic phenol formaldehyde compound that is effective as a selective adsorbent for heavy metal ions and has excellent heat resistance, and a method for producing the same. Conventional adsorbents for heavy metal ions such as copper, mercury, and nickel contained in various wastewaters include activated carbon, diatomaceous earth, various ion exchange resins, and resins with chelating ability, such as various crown ether compounds. However, activated carbon, diatomaceous earth, and ion exchange resins have poor selectivity for heavy metal ions, and crown ether compounds have some selectivity but have poor heat resistance, are expensive, and lack versatility. It was hot. The present invention provides a novel heptacyclic phenol formaldehyde resin that has extremely excellent selective adsorption ability for heavy metal ions, is inexpensive, and has high heat resistance. That is, the present invention is based on the general formula [In the formula, R is CnH 2 n+1 (n=an integer of 0 to 10). ] It provides heptacyclic phenol formaldehyde resins represented by the following. The characteristic of the resin represented by the above general formula is that seven molecules of phenol substituted with a specific group at the rose position form a cyclic body with the hydroxyl group facing inward via seven methylene groups, and it is almost cyclic. The hydroxyl group located in the molecule coordinates with the heavy metal ion and exhibits selective adhesion. Additionally, this compound has heat resistance and can be produced at low cost. R in the formula is hydrogen or an alkyl group having 0 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, or an octyl group. If R is an alkyl group having 11 or more carbon atoms, a cyclic body will not be formed, and therefore, selective adsorption for heavy metal ions will not be exhibited. Next, a general method for preparing the novel compounds of the present invention will be described. First, 1.2 to 3.0 moles of formaldehyde are mixed with 1 mole of phenols, and a non-aqueous solvent of 2 to 4 times the weight of the phenols is added to suspend the mixture, and then an alkali metal hydroxide is added to the phenols. 0.05 to 0.5 mol% of the solvent is preferably dissolved in water and the reaction temperature is
React at 100-120℃ for 30-100 hours. Structural formula for phenols
【式】〔Ｒ＝CnH2n+1（ｎ＝
０〜10）〕なるフエノール類が用いられ、好まし
くはｐ−フエニルフエノール、が用いられる。
ホルムアルデヒド類としては、反応時にホルム
アルデヒドを発生するパラホルムアルデヒド等が
用いられる。
アルカリ金属の水酸化物としてはNa、Ｋ、
Rb、Cs、Frの水酸化物が、非水系溶媒としては
ベンゼン、トルエン、キシレン、ヘプタン、ジオ
キサン等が用いられる。
得られた反応混合物は希塩酸等の鉱酸を加えて
酸性とし減圧下で溶剤を留去し固体を得る。そし
て本発明の化合物は例えば次のようにして精製さ
れる。
得られた固体をクロロホルムに溶解し徐々にメ
タノールを添加して分別再結晶法で各フラクシヨ
ンに分離する。フエノール類の７環状体に相当す
る分子量のフラクシヨンについてシリカゲル吸着
クロマトグラフイーで精製する。
即ち、吸着剤としてシリカゲル（ワコーゲル
C300和光純薬社商品名）を使用しクロロホルム
−ｎヘキサン（１：１−vol％）を溶離液として
初期の溶出物を分離する。
この分離液を減圧下で溶剤を留去し本発明の化
合物が粉末状の固体として得られる。
次に本発明の７環状体フエノール・ホルムアル
デヒド樹脂の合成例を示す。
実施例 １
ｐ−フエニルフエノール68.4ｇ（0.4モル）と
パラホルムアルデヒド30ｇ（0.8モル）をジオキ
サン200mlに懸濁さ、水酸化カリウム4.5ｇ（約
0.08モル）を水２mlに溶解したものを加え、反応
温度110℃（還流下で）48時間、反応させた。約
25時間後より固体が析出しはじめた。
固体を含む反応混合液を希塩酸を加えて酸性と
し、溶媒を減圧下で留去し固体を得た。
こうして得た固体をクロロホルムに溶解し徐々
にメタノールを添加して溶媒組成を変えて分別再
結晶法で５つのフラクシヨンに分離する。それぞ
れの組成の概要は次の通りであつた。
フラクシヨン１：８環状体
フラクシヨン２：８環状体＋６環状体
フラクシヨン３：７還状体＋少量の線状オリゴ
マー混合物
フラクシヨン４：少量の７環状体＋線状オリゴ
マー
フラクシヨン５：線状オリゴマー
ついてフラクシヨン３について、シリカゲル
（ワコーゲルC300）を吸着剤にクロロホルム−ｎ
−ヘキサン（１：１体積％）を溶離液としたシリ
カゲル吸着クロマトグラフイーで初期溶出物を採
取精製した。
このものの分析結果は次の通りであつた。
１ 融点 ＞310℃ 融解せず測定不能
（環状体の特徴）
２ 分子量 1274と一致
３ マススペクトル（70eV）
ｍ／ｅ 1274（M+）
４ 核磁気共鳴スペクトル
（四塩化炭素 溶媒、TMS基準）
δ（ppm）10.付近
（シヤープな単一ピーク−OH）
（環状体の特徴）
7.4〜7.2 7.1
（シヤープな多重ピークRing−Ｈ）
3.9（ブロードな単一ピーク−CH2−）
５ 赤外線吸収スペクトル（KBr錠剤法）
波数（cm-1）3200（水素結合−OH）
（環状体の特徴）
以上の結果から得られた結晶は
であることがわかつた。
実施例 ２
４−ヒドロキシ4′−メチルビフエニル73.6ｇ
（0.4モル）とパラホルムアルデヒド37.5ｇ（1.0モ
ル）をジオキサン150mlに懸濁させ水酸化ナトリ
ウム1.6ｇ（0.04モル）を水1.5mlに溶解したもの
を加え反応温度110℃（還流下で）36時間反応さ
せた。ついで固体を含む反応混合液に希塩酸を加
えて酸性とし溶媒を減圧下で留去し固体を得た。
以下、実施例１記載の方法で分別再結晶および
シリカゲル吸着クロマトグラフイーで７環状体を
採取精製した。
このものの分析結果は次の通りであつた。
１ 融点 ＞310 融解せず測定不能
（環状体の特徴）
２ 分子量 1372と一致
３ マススペクトル（70eV）
ｍ／ｅ 1372（M+）
４ 核磁気共鳴スペクトル
（重クロロホルム溶媒、TMS基準）
δ（ppm）10.0付近
（シヤープな単一ピーク、−ＯＨ）
（環状体の特徴）
7.4〜7.1 （シヤープな多重ピーク、Ring-
Ｈ）
3.9 （ブロードな単一ピーク、−ＣＨ ２−）
2.3 （シヤープなピーク、−ＣＨ ３−）
５ 赤外線吸収スペクトル（KBr錠剤法）
波数（cm-1）3200（水素結合、−OH）
（環状体の特徴）
以上の結果から得られた結晶は
であることがわかつた。
実施例 ３
４−ヒドロキシ4′−オクチルビフエニル109ｇ
（0.4モル）とパラホルムアルデヒド30ｇ（0.8モ
ル）をジオキサン200mlに撹拌混合させ水酸化ナ
トリウム1.6ｇ（0.04モル）を水2.0mlに溶解した
ものを加え、反応温度110℃（環流下で）48時間
反応させた。ついで固体を含む反応混合液に希塩
酸を加えて酸性とし、溶媒を減圧下で留去し固形
物を得た。
以下実施例１記載の方法で分別再結晶およびシ
リカゲル吸着クロマトグラフイーで７環状体を採
取精製した。
このものの分析結果は次の通りであつた。
１ 融点 ＞310℃融解せず測定不能
（環状体の特徴）
２ 分子量 2002と一致
３ マスペクトル（70eV）ｍ／e2002（M+）
４ 核磁気共鳴スペクトル
（重クロロホルム溶媒、TMS基準）
δ（ppm） 10付近（シヤープな単一ピー
ク、−OH）
7.4〜7.2，7.1（シヤープな多重ピーク、
Ring−Ｈ）
3.9付近（ブロードな単一ピーク、−CH2−）
2.3付近（シヤープなピーク、−CH3−）
５ 赤外線吸収スペクトル（KBr錠剤法）
波数（cm-1） 3200付近
（水素結合した−OH）
以上の結果から得られた結晶は
であることがわかつた。A phenol having the formula [R=CnH 2 n +1 (n=0 to 10)] is used, and p-phenylphenol is preferably used. As the formaldehyde, paraformaldehyde, which generates formaldehyde during reaction, is used. Alkali metal hydroxides include Na, K,
Hydroxides of Rb, Cs, and Fr are used, and benzene, toluene, xylene, heptane, dioxane, etc. are used as non-aqueous solvents. The resulting reaction mixture is made acidic by adding a mineral acid such as dilute hydrochloric acid, and the solvent is distilled off under reduced pressure to obtain a solid. The compound of the present invention is then purified, for example, as follows. The obtained solid is dissolved in chloroform, methanol is gradually added and separated into fractions by fractional recrystallization. A fraction with a molecular weight corresponding to a heptacyclic phenol is purified by silica gel adsorption chromatography. That is, silica gel (Wako gel) was used as an adsorbent.
C300 (trade name, Wako Pure Chemical Industries, Ltd.) was used to separate the initial eluate using chloroform-n-hexane (1:1-vol%) as the eluent. The solvent of this separated liquid is distilled off under reduced pressure to obtain the compound of the present invention as a powdery solid. Next, a synthesis example of the heptacyclic phenol formaldehyde resin of the present invention will be shown. Example 1 68.4 g (0.4 mol) of p-phenylphenol and 30 g (0.8 mol) of paraformaldehyde were suspended in 200 ml of dioxane, and 4.5 g (approx.
A solution of 0.08 mol) in 2 ml of water was added, and the mixture was reacted at a reaction temperature of 110°C (under reflux) for 48 hours. about
After 25 hours, solids began to precipitate. The reaction mixture containing the solid was made acidic by adding dilute hydrochloric acid, and the solvent was distilled off under reduced pressure to obtain a solid. The solid thus obtained is dissolved in chloroform, methanol is gradually added to change the solvent composition, and the solution is separated into five fractions by fractional recrystallization. The outline of each composition was as follows. Fraction 1: 8 cyclic body Fraction 2: 8 cyclic body + 6 cyclic body Fraction 3: 7 cyclic body + a small amount of linear oligomer mixture Fraction 4: A small amount of 7 cyclic body + linear oligomer Fraction 5: Linear oligomer Fraction 3 chloroform-n using silica gel (Wako Gel C300) as an adsorbent.
- The initial eluate was collected and purified by silica gel adsorption chromatography using hexane (1:1% by volume) as the eluent. The analysis results of this product were as follows. 1 Melting point ＞310℃ Cannot be measured because it does not melt (Characteristics of cyclic body) 2 Molecular weight Matches 1274 3 Mass spectrum (70eV)
m/e 1274 (M + ) 4 nuclear magnetic resonance spectrum
(Carbon tetrachloride solvent, TMS standard) δ (ppm) around 10.
(Sharp single peak -OH) (Characteristics of cyclic body) 7.4-7.2 7.1
(Sharp multiple peaks Ring-H) 3.9 (Broad single peak - CH 2 -) 5 Infrared absorption spectrum (KBr tablet method) Wavenumber (cm -1 ) 3200 (Hydrogen bond -OH) (Characteristics of cyclic body) Above The crystal obtained from the result is It turns out that it is. Example 2 4-hydroxy 4'-methylbiphenyl 73.6g
(0.4 mol) and 37.5 g (1.0 mol) of paraformaldehyde were suspended in 150 ml of dioxane, 1.6 g (0.04 mol) of sodium hydroxide dissolved in 1.5 ml of water was added, and the reaction temperature was 110°C (under reflux) for 36 hours. Made it react. Then, dilute hydrochloric acid was added to the reaction mixture containing the solid to make it acidic, and the solvent was distilled off under reduced pressure to obtain a solid. Thereafter, the 7-ring compound was collected and purified by fractional recrystallization and silica gel adsorption chromatography using the method described in Example 1. The analysis results of this product were as follows. 1 Melting point >310 Unmeasurable as it does not melt (Characteristics of a cyclic body) 2 Molecular weight Matches 1372 3 Mass spectrum (70eV)
m/e 1372 (M + ) 4 nuclear magnetic resonance spectrum
(Deuterated chloroform solvent, TMS standard) δ (ppm) around 10.0
(Sharp single peak, -OH ) (Characteristics of a ring) 7.4~7.1 (Sharp multiple peaks, Ring -
H ) 3.9 (Broad single peak, -CH 2 -) 2.3 (Sharp peak, -CH 3 -) 5 Infrared absorption spectrum (KBr tablet method) Wavenumber (cm -1 ) 3200 (Hydrogen bond, -OH ) (Characteristics of cyclic bodies) The crystal obtained from the above results is It turns out that it is. Example 3 4-hydroxy 4'-octylbiphenyl 109g
(0.4 mol) and 30 g (0.8 mol) of paraformaldehyde were stirred and mixed in 200 ml of dioxane, 1.6 g (0.04 mol) of sodium hydroxide dissolved in 2.0 ml of water was added, and the reaction temperature was 110°C (under reflux) for 48 hours. Made it react. Then, dilute hydrochloric acid was added to the reaction mixture containing the solid to make it acidic, and the solvent was distilled off under reduced pressure to obtain a solid. Hereinafter, the 7-ring compound was collected and purified by fractional recrystallization and silica gel adsorption chromatography as described in Example 1. The analysis results of this product were as follows. 1 Melting point ＞310℃ Cannot be measured without melting
(Characteristics of cyclic bodies) 2 Molecular weight Matches 2002 3 Mass spectrum (70eV) m/e2002 (M + ) 4 Nuclear magnetic resonance spectrum
(Deuterated chloroform solvent, TMS standard) δ (ppm) around 10 (sharp single peak, -OH) 7.4 to 7.2, 7.1 (sharp multiple peaks,
Ring-H) Around 3.9 (broad single peak, -CH 2 -) Around 2.3 (sharp peak, -CH 3 -) 5 Infrared absorption spectrum (KBr tablet method) Wavenumber (cm -1 ) Around 3200
(Hydrogen-bonded -OH) The crystal obtained from the above results is It turns out that it is.
Claims (1)
である。〕 で表わされる７環状フエノール・ホルムアルデヒ
ド化合物。 ２ Ｒが−Ｈである特許請求範囲第１項記載の７
環状フエノール・ホルムアルデヒド化合物。 ３ 構造式【式】〔Ｒ＝ CnH2n+1−（ｎ＝０〜10）〕なるフエノール類１モ
ルに対しホルムアルデヒド類を1.2〜3.0モル配合
し、これにフエノール類に対して２〜４重量倍の
非水系溶媒を加えて懸濁させ、ついでアルカリ金
属の水酸化物をフエノール類に対して0.05〜0.5
モル％添加し、100〜120℃で30〜100時間反応さ
せることを特徴とする７環状フエノールホルム・
アルデヒド化合物の製造法。[Claims] 1. General formula [In the formula, R is CnH 2 n+1) (n = integer from 0 to 10)
It is. ] A heptacyclic phenol formaldehyde compound represented by: 2. 7 of Claim 1, wherein R is -H
Cyclic phenol formaldehyde compound. 3. 1.2 to 3.0 mol of formaldehyde is blended to 1 mol of phenols with the structural formula [Formula] [R = CnH 2 n +1 - (n = 0 to 10)], and this is mixed with 2 to 4 mol of formaldehyde based on the phenol. Add twice the weight of a non-aqueous solvent to suspend it, then add alkali metal hydroxide to the phenols at a ratio of 0.05 to 0.5.
7-cyclic phenolform, which is characterized by adding mol% and reacting at 100-120°C for 30-100 hours.
Method for producing aldehyde compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21412982A JPS59104332A (en) | 1982-12-07 | 1982-12-07 | Cyclic phenol-formaldehyde compound constituted of seven ring-forming units and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21412982A JPS59104332A (en) | 1982-12-07 | 1982-12-07 | Cyclic phenol-formaldehyde compound constituted of seven ring-forming units and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59104332A JPS59104332A (en) | 1984-06-16 |
| JPS625410B2 true JPS625410B2 (en) | 1987-02-04 |
Family
ID=16650698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21412982A Granted JPS59104332A (en) | 1982-12-07 | 1982-12-07 | Cyclic phenol-formaldehyde compound constituted of seven ring-forming units and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59104332A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62173634A (en) * | 1986-01-28 | 1987-07-30 | Alpine Electron Inc | Track jump detector |
| JP4576316B2 (en) | 2005-10-20 | 2010-11-04 | 株式会社日立製作所 | Servo control signal generation apparatus, optical disc apparatus, and servo control signal generation method |
| JP2010192105A (en) * | 2010-04-19 | 2010-09-02 | Hitachi Ltd | Apparatus for generating servo control signal, optical disk apparatus, and method for generating servo control signal |
-
1982
- 1982-12-07 JP JP21412982A patent/JPS59104332A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59104332A (en) | 1984-06-16 |
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