JPH0377186B2 - - Google Patents
Info
- Publication number
- JPH0377186B2 JPH0377186B2 JP10135883A JP10135883A JPH0377186B2 JP H0377186 B2 JPH0377186 B2 JP H0377186B2 JP 10135883 A JP10135883 A JP 10135883A JP 10135883 A JP10135883 A JP 10135883A JP H0377186 B2 JPH0377186 B2 JP H0377186B2
- Authority
- JP
- Japan
- Prior art keywords
- hydroxy
- sulfone
- benzyloxydiphenyl
- mbe
- benzyloxydiphenyl sulfone
- 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
- 150000003457 sulfones Chemical class 0.000 claims description 10
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000005325 alkali earth metal hydroxides Chemical class 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000004807 phenyl sulfones Chemical class 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は４−ヒドロキシ−4′−ベンジルオキシ
ジフエニルスルホン
の製法に関す。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 4-hydroxy-4'-benzyloxydiphenyl sulfone Regarding the manufacturing method.
４−ヒドロキシ−4′−ベンジルオキシジフエニ
ルスルホン（以下BS−MBEという）は公知の化
合物であつて写真材料等に用いられる有用な原料
である。 4-Hydroxy-4'-benzyloxydiphenyl sulfone (hereinafter referred to as BS-MBE) is a known compound and a useful raw material used in photographic materials and the like.
本発明者はフエニルスルホン類について従来か
ら研究を続けて来たが、この研究に於いてBS−
MBEの製造法の開発に成功し、茲に本発明を完
成するに至つた。即ち本発明は４，4′−ジヒドロ
キシジフエニルスルホン１モルを、アルカリ金属
または（及び）アルカリ土類金属の水酸化物また
は（及び）塩0.8〜1.2当量含む水に溶解せしめ、
40〜80℃で塩化ベンジル0.8〜1.2当量と反応せし
めて析出する４−ヒドロキシ−4′−ベンジルオキ
シジフエニルスルホンを分離することを特徴とす
る４−ヒドロキシ−4′−ベンジルオキシジフエニ
ルスルホンの製造法に係るものである。 The present inventor has been conducting research on phenyl sulfones for a long time, and in this research, BS-
We succeeded in developing a method for producing MBE, and finally completed the present invention. That is, in the present invention, 1 mole of 4,4'-dihydroxydiphenyl sulfone is dissolved in water containing 0.8 to 1.2 equivalents of an alkali metal or (and) alkaline earth metal hydroxide or (and) salt,
4-hydroxy-4'-benzyloxydiphenyl sulfone, which is characterized by separating 4-hydroxy-4'-benzyloxydiphenyl sulfone precipitated by reaction with 0.8 to 1.2 equivalents of benzyl chloride at 40 to 80°C. This relates to the manufacturing method.
本発明法は目的物４−ヒドロキシ−4′−ベンジ
ルオキシジフエニルスルホンを溶剤を使用するこ
となく分離するものであり、またジベンジル体の
副生を極めて効率良く抑制することが出来る特徴
を有する。 The method of the present invention is capable of separating the target product, 4-hydroxy-4'-benzyloxydiphenyl sulfone, without using a solvent, and is characterized in that it can very efficiently suppress the by-product of dibenzyl derivatives.
本発明に於いては原料として使用する塩化ベン
ジル及び４，4′−ジヒドロキシジフエニルスルホ
ンの使用割合が、後者１モルに対し前者0.8〜1.2
当量とすることを必須とする。この際前者が0.8
当量に達しない場合は原料４，4′−ジヒドロキシ
ジフエニルスルホンの残存量が多くなり収率が下
る傾向があり、また1.2当量より多くなるとジベ
ンジル体の副生が多くなる傾向がある。また本発
明に於いてはアルカリ金属または（及び）アルカ
リ土類金属の水酸化物または（及び）塩の使用量
も極めて重要であり、４，4′−ジヒドロキシジフ
エニルスルホン１モルに対し0.8〜1.2当量使用す
る必要がある。この際0.8当量に達しない場合及
び1.2当量より多くなる場合はいずれも上記と同
様な傾向を有す。使用されるアルカリ金属または
（及び）アルカリ土類金属の水酸化物及び塩とし
ては、たとえばNaOH、KOH、LiOH、
Na2CO3、K2CO3、Ca（OH）2、Mg（OH）2等を例
示出来、好ましいものとしてNaOHを挙げるこ
とが出来る。 In the present invention, the ratio of benzyl chloride and 4,4'-dihydroxydiphenyl sulfone used as raw materials is 0.8 to 1.2 mol of the former to 1 mol of the latter.
It is essential that the amount be equivalent. In this case, the former is 0.8
If the equivalent amount is not reached, the remaining amount of the raw material 4,4'-dihydroxydiphenylsulfone tends to increase and the yield tends to decrease, and if the amount exceeds 1.2 equivalents, the by-product of dibenzyl compounds tends to increase. In addition, in the present invention, the amount of alkali metal or (and) alkaline earth metal hydroxide or (and) salt used is also extremely important, and is 0.8 to 0.8 to 1 mole of 4,4'-dihydroxydiphenylsulfone. 1.2 equivalents should be used. In this case, both cases in which the amount does not reach 0.8 equivalents and cases in which the amount exceeds 1.2 equivalents have the same tendency as described above. The hydroxides and salts of alkali metals and/or alkaline earth metals used include, for example, NaOH, KOH, LiOH,
Examples include Na 2 CO 3 , K 2 CO 3 , Ca(OH) 2 , Mg(OH) 2 and the like, with NaOH being preferred.
本発明法に於いてはこれ等特定量の両原料及び
アルカリ金属または土類金属の水酸化物または
（及び）塩を使用し、且つ40〜80℃という特定の
温度で反応を行う必要があり、これにより溶剤を
使用することなく目的物BS−MBEを分離するこ
とが出来ると共に望ましくない副生物たるジベン
ジル体の生成を極めて有効に抑制出来るのであ
る。 In the method of the present invention, it is necessary to use specific amounts of both raw materials and alkali metal or earth metal hydroxides or (and) salts, and to carry out the reaction at a specific temperature of 40 to 80°C. As a result, the target product BS-MBE can be separated without using a solvent, and the formation of dibenzyl compounds as undesirable by-products can be extremely effectively suppressed.
本発明に於いては、上記条件により反応を行う
ことにより４−ヒドロキシ−4′−ベンジルオキシ
−ジフエニルスルホンを製造することが出来る。 In the present invention, 4-hydroxy-4'-benzyloxy-diphenyl sulfone can be produced by carrying out the reaction under the above conditions.
また本発明に於いては、かくして得られた４−
ヒドロキシ−4′−ベンジルオキシ−ジフエニルス
ルホンを更に精製して次の様な処理により、より
一層純度を向上せしめることも出来る。先ず上記
４−ヒドロキシ−4′−ベンジルオキシ−ジフエニ
ルスルホン１モルに当し、0.8〜2.0当量のアルカ
リ金属または土類金属の水酸化物及び塩を含む水
中に溶解し、次いで50℃以上の温度で酸性物質に
よりPHを8.5〜10.0になるまで部分中和する。BS
−MBGが析出して来る。この処理に依り４−ヒ
ドロキシ−4′−ベンジルオキシ−ジフエニルスル
ホンの純度が著しく向上する。この際のアルカリ
金属または土類金属の水酸化物または（及び）塩
の使用割合が上記範囲に達しない場合はBS−
MBEの溶解性が減少する。 Further, in the present invention, the thus obtained 4-
Hydroxy-4'-benzyloxy-diphenyl sulfone can be further purified and the purity can be further improved by the following treatment. First, 1 mole of the above 4-hydroxy-4'-benzyloxy-diphenyl sulfone is dissolved in water containing 0.8 to 2.0 equivalents of alkali metal or earth metal hydroxide and salt, and then heated to 50°C or higher. Partially neutralize the pH with acidic substances at temperature to 8.5-10.0. B.S.
-MBG begins to precipitate. This treatment significantly improves the purity of 4-hydroxy-4'-benzyloxy-diphenylsulfone. If the proportion of alkali metal or earth metal hydroxides or (and) salts used in this case does not reach the above range, BS-
The solubility of MBE decreases.
また酸性物質により部分中和する際の中和程度
はPH8.5〜10.0になる範囲である。このPH範囲は
極めて重要であり8.5に達しない場合及び10.0よ
りも高くなると所期の目的を達成出来ない。この
際使用する酸性物質としてはたとえば硫酸、塩酸
等を例示出来る。 Further, when partially neutralizing with an acidic substance, the degree of neutralization is in the range of PH8.5 to 10.0. This PH range is extremely important, and if it does not reach 8.5 or exceeds 10.0, the intended purpose cannot be achieved. Examples of acidic substances used in this case include sulfuric acid and hydrochloric acid.
実施例 １
４，4′−ジヒドロキシジフエニルスルホン
250.3ｇ（1.00モル）を、苛性ソーダ40.8ｇ（1.02
モル）を含有する2.5の水に60℃で溶解せしめ
た後、同温度で塩化ベンジル126.6ｇ（1.00モル）
を８時間を要して滴下した。更に同温度で４時間
保温後40℃まで冷却し析出したBS−MBEを別
した。収量313ｇ、収率（対４，4′−ジヒドロキ
シジフエニルスルホン）92％、BS−MBE純度97
％で融点166.0〜169.0℃であつた。Example 1 4,4'-dihydroxydiphenyl sulfone
250.3g (1.00mol), 40.8g (1.02mol) of caustic soda
126.6 g (1.00 mol) of benzyl chloride was dissolved at 60°C in water containing 2.5 mol) of
was added dropwise over a period of 8 hours. After further incubating at the same temperature for 4 hours, it was cooled to 40°C and the precipitated BS-MBE was separated. Yield 313g, yield (based on 4,4'-dihydroxydiphenylsulfone) 92%, BS-MBE purity 97
%, the melting point was 166.0-169.0°C.
実施例 ２
上記実施例１と同様の方法で製造したBS−
MBE340ｇをNaOH44ｇ（1.1モル）を含有する
3.5の水に90℃にて溶解させ、活性炭10ｇを加
えて不溶性不純物を熱時ろ過後、製品の酸化防止
剤としての還元剤ハイドロサルフアイト1.0ｇ及
び金属汚染防止剤としてのキレート剤EDTA3.0
ｇを添加後、90℃の温度において78％硫酸により
PHが9.3になるまで中和した。後40℃まで冷却し
て析出しているBS−MBEをろ別した。Example 2 BS- produced in the same manner as in Example 1 above
Contains 340g MBE and 44g (1.1 mol) NaOH
3.5 in water at 90℃, add 10g of activated carbon, and filter out insoluble impurities while hot.The product contains 1.0g of reducing agent hydrosulfite as an antioxidant and 3.0 chelating agent EDTA as a metal pollution inhibitor.
With 78% sulfuric acid at a temperature of 90 °C after adding g
Neutralized until pH reached 9.3. After cooling to 40°C, precipitated BS-MBE was filtered off.
収量289ｇ。対BS−MBE収率85％。BS−
MBE純度99.5％HPLC分析。融点168.0〜170.0
℃。 Yield 289g. Yield of BS-MBE is 85%. BS−
MBE purity 99.5% HPLC analysis. Melting point 168.0~170.0
℃.
Claims (1)
モルを、アルカリ金属または（及び）アルカリ土
類金属の水酸化物または（及び）塩0.8〜1.2当量
含む水に溶解せしめ、40〜80℃で塩化ベンジル
0.8〜1.2当量と反応せしめて析出する４−ヒドロ
キシ−4′−ベンジルオキシジフエニルスルホンを
分離することを特徴とする４−ヒドロキシ−4′−
ベンジルオキシジフエニルスルホンの製造法。 ２ 上記特許請求の範囲第１項の製造法に依り製
造された４−ヒドロキシ−4′−ベンジルオキシジ
フエニルスルホンをアルカリ金属またはアルカリ
土類金属の水酸化物または（及び）塩を含む水に
溶解せしめ、50℃以上の温度で酸性物質によりPH
8.5〜10.0になるまで部分中和して析出する４−
ヒドロキシ−4′−ベンジルオキシジフエニルスル
ホンを分離することを特徴とする４−ヒドロキシ
−4′−ベンジルオキシジフエニルスルホンの製造
法。[Claims] 1 4,4'-dihydroxydiphenyl sulfone 1
benzyl chloride at 40 to 80°C.
4-hydroxy-4'-, which is characterized by separating 4-hydroxy-4'-benzyloxydiphenyl sulfone precipitated by reaction with 0.8 to 1.2 equivalents.
Method for producing benzyloxydiphenyl sulfone. 2. 4-Hydroxy-4'-benzyloxydiphenyl sulfone produced by the production method of claim 1 above is added to water containing an alkali metal or alkaline earth metal hydroxide or (and) salt. Dissolve and adjust the pH using an acidic substance at a temperature of 50°C or higher.
Partially neutralize and precipitate until it reaches 8.5-10.0 4-
A method for producing 4-hydroxy-4'-benzyloxydiphenyl sulfone, which comprises separating hydroxy-4'-benzyloxydiphenyl sulfone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10135883A JPS59225157A (en) | 1983-06-06 | 1983-06-06 | Preparation of 4-hydroxy-4'-benzyloxydiphenylsulfone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10135883A JPS59225157A (en) | 1983-06-06 | 1983-06-06 | Preparation of 4-hydroxy-4'-benzyloxydiphenylsulfone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59225157A JPS59225157A (en) | 1984-12-18 |
| JPH0377186B2 true JPH0377186B2 (en) | 1991-12-09 |
Family
ID=14298607
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10135883A Granted JPS59225157A (en) | 1983-06-06 | 1983-06-06 | Preparation of 4-hydroxy-4'-benzyloxydiphenylsulfone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59225157A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101421617B1 (en) * | 2013-08-30 | 2014-07-22 | 우리이티아이 주식회사 | Method of manufacturing printed circuit board |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5001270A (en) * | 1985-10-04 | 1991-03-19 | Amoco Corporation | Process for recovering 4,4' dihydroxydiphenyl sulfone from an isomer mixture |
| EP0465665B1 (en) * | 1990-01-29 | 1995-04-12 | Yoshitomi Pharmaceutical Industries, Ltd. | Process for producing diphenyl sulfone compound |
| US5284978A (en) * | 1990-01-29 | 1994-02-08 | Yoshitomi Pharmaceutical Industries, Ltd. | Method for producing diphenyl sulfone compounds |
| JP3169574B2 (en) * | 1997-12-24 | 2001-05-28 | 日華化学株式会社 | Method for producing 4-hydroxy-4'-benzyloxydiphenyl sulfone |
| JP2018016000A (en) * | 2016-07-28 | 2018-02-01 | 日華化学株式会社 | Method for producing color developing composition for heat-sensitive recording, color developing composition for heat-sensitive recording, and heat-sensitive recording material |
-
1983
- 1983-06-06 JP JP10135883A patent/JPS59225157A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101421617B1 (en) * | 2013-08-30 | 2014-07-22 | 우리이티아이 주식회사 | Method of manufacturing printed circuit board |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59225157A (en) | 1984-12-18 |
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