JPH0551569B2 - - Google Patents
Info
- Publication number
- JPH0551569B2 JPH0551569B2 JP1376886A JP1376886A JPH0551569B2 JP H0551569 B2 JPH0551569 B2 JP H0551569B2 JP 1376886 A JP1376886 A JP 1376886A JP 1376886 A JP1376886 A JP 1376886A JP H0551569 B2 JPH0551569 B2 JP H0551569B2
- Authority
- JP
- Japan
- Prior art keywords
- formula
- acid
- reaction
- dichlorophenols
- chloride
- 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 - Lifetime
Links
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical class OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- -1 p-substituted dichlorophenols Chemical class 0.000 description 14
- 239000000243 solution Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 238000005660 chlorination reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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 class C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012320 chlorinating reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 1
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- SANZGCKGKOUHJG-UHFFFAOYSA-N 2,3-dichloro-4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C(Cl)=C1Cl SANZGCKGKOUHJG-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- BOFRXDMCQRTGII-UHFFFAOYSA-N 619-08-9 Chemical compound OC1=CC=C([N+]([O-])=O)C=C1Cl BOFRXDMCQRTGII-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- REZZEXDLIUJMMS-UHFFFAOYSA-M dimethyldioctadecylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC REZZEXDLIUJMMS-UHFFFAOYSA-M 0.000 description 1
- 239000004664 distearyldimethylammonium chloride (DHTDMAC) Substances 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
産業上の利用分野
本発明はジクロロフエノール類の製造法に関す
る。
更に詳しくは、ｐ−置換フエノール類又はそれ
らの塩類をジクロル化することによるｐ−置換ジ
クロロフエノール類の製造法に関する。
従来の技術
ジクロロフエノール類は医・農薬、染・顔料の
原料として重要な化合物である。フエノール類の
クロル化法としては、
(1) 塩素ガスを用い溶媒存在下、もしくは無溶媒
下クロル化する方法（特開昭57−70840、BP−
573477等）
(2) 塩化スルフリルを用い高温下でクロル化する
方法（SOP、４巻、236等）
(3) 塩酸を含む溶媒中、過酸化水素を作用させて
クロル化する方法（特開昭60−56939等）
(4) 塩素酸ソーダと塩酸を作用させクロル化する
方法（PB−ReportNo.781、Schweiz Ｐ−
163887等）
(5) アルカリ性水溶液下、次亜塩素酸塩を作用さ
せクロル化する方法（DRP−167458、C.A.41
巻（1947）734等）
等が知られている。
発明が解決しようとする問題点
ジクロロフエノール類を製造する方法として公
知の前記した各方法においては、種々の欠点があ
る。即ち(1)法は塩素ガスを使用する為特別な反応
器を要し、又、オフガスの除害設備を要するなど
生産設備上の制約がある。(2)法いついては、高価
な塩化スルフリルを用いることによるコスト上の
問題のみならず該薬剤は安全性、毒性の面で取扱
いが厄介である、(3)法については廃塩酸の処理、
過酸化水素の安全性等に問題が残る、(4)法につい
ては、塩素酸ソーダの薬剤費及び安全性に問題が
残る、(5)法についれは、アルカリ性下で次亜塩素
酸塩が比較的安定である為、クロル化において反
応条件を厳しくする必要がありその為、原料又は
目的物の酸化反応がおこり副生物の増加がみられ
る等である。
このような理由からフエノール類のクロル化に
よるジクロロフエノール類を製造するにあたり、
安価に、収率よく、安全に、そして工業的な意味
から容易にジクロロフエノール類を製造する方法
の開発が望まれている。
問題点を解決するための手段
本発明は前記したような問題点のないジクロロ
フエノール類とりわけｐ−置換ジクロロフエノー
ル類の製法につき鋭意研究を重ねた結果、本発明
に至つたものである。
即ち、本発明は、式(1)
（式(1)においてR1はハロゲン、C1〜4のアルキ
ル、ニトロ又はカルボキシルを、R2は水素、ナ
トリウム、カリウム又はリチウムを表す）で表さ
れる化合物に分散剤又は／及びルイス酸の存在下
PH2.0〜7.0で次亜塩素酸又は／及びその塩を反応
させることを特徴とする式(2)
（式(2)において、R1は前記と同じ意味を表す）
で表されるジクロロフエノール類の製造方法を提
供するものである。
本発明の方法を詳細に説明する。
本発明の方法においては反応媒体として水が用
いられ、その使用量は原料のｐ−置換フエノール
類に対して２〜10倍好ましくは３〜５倍（重量
比）である。なお反応液の粘度を下げる目的で水
にその20％（容量）以下のジクロルメタン、テト
ラクロルエタン等のハロゲン化脂肪族炭化水素を
加えることもできる。
本発明の方法で使用する分散剤としてはノニオ
ン系、カチオン系又はアニオン系の分散剤が用い
られ、その具体例としては例えば、POE（ポリオ
キシエチレン）ラウリルエーテル、POE高級ア
ルコールエーテル、POEオクチルフエニルエー
テル、POEノニルフエニルエーテル、エチレン
ジアミンのPOE・POP（ポリオキシプロピレン）
縮合物等のPOE又はPOP誘導体、又、セチルト
リメチルアンモニウムクロライド、ラウリルトリ
メチルアンモニウムクロライド、ステアリルトリ
メチルアンモニウムクロライド、ジステアリルジ
メチルアンモニウムクロライド等の第四級アンモ
ニウム塩、又、アルキルメチルタウライド、ホル
マリンナフタリンスルホン酸の縮合物等が挙げら
れる。
上記分散剤は反応液量に対して用いられ必要に
応じ0.01％〜10％（重量／容量）好ましくは0.1
％〜３％（重量／容量）用いられる。本発明で用
いられるルイス酸の具体例としては塩化第二鉄、
塩化アルミニウム、塩化亜鉛、塩化マグネシウ
ム、塩化スズ等が挙げられるが、取扱い、コスト
の点より塩化第二鉄、塩化アルミニウムの使用が
望ましい。その使用量は、反応基質に対し0.01〜
20モル％がよく更に好ましくは0.1〜10モル％が
よい。
本発明の方法においては前記した分散剤及びル
イス酸を両方とも用いてもよいし又いずれか一方
のみ用いてもよい。
本発明の方法において原料として使用するｐ−
置換フエノール類の具体例としては次のようなも
の
INDUSTRIAL APPLICATION FIELD The present invention relates to a method for producing dichlorophenols. More specifically, the present invention relates to a method for producing p-substituted dichlorophenols by dichlorinating p-substituted phenols or salts thereof. BACKGROUND OF THE INVENTION Dichlorophenols are important compounds as raw materials for medicines, agricultural chemicals, dyes, and pigments. Methods for chlorinating phenols include: (1) Chlorination using chlorine gas in the presence of a solvent or in the absence of a solvent (Japanese Unexamined Patent Publication No. 57-70840, BP-
573477, etc.) (2) A method of chlorination at high temperatures using sulfuryl chloride (SOP, Vol. 4, 236, etc.) (3) A method of chlorination using hydrogen peroxide in a solvent containing hydrochloric acid (JP-A-Sho) 60-56939, etc.) (4) Method of chlorination by reacting sodium chlorate and hydrochloric acid (PB-Report No. 781, Schweiz P-
163887, etc.) (5) Method of chlorination using hypochlorite in an alkaline aqueous solution (DRP-167458, CA41
Volume (1947) 734, etc.) are known. Problems to be Solved by the Invention The above-mentioned known methods for producing dichlorophenols have various drawbacks. That is, method (1) requires a special reactor because it uses chlorine gas, and has limitations in terms of production equipment, such as requiring off-gas abatement equipment. (2) Regarding the method, there are not only cost problems due to the use of expensive sulfuryl chloride, but also that the drug is difficult to handle in terms of safety and toxicity. (3) Regarding the method, the treatment of waste hydrochloric acid,
Problems remain regarding the safety of hydrogen peroxide, etc. Regarding method (4), problems remain regarding the chemical costs and safety of sodium chlorate; and regarding method (5), hypochlorite does not react in alkaline conditions. Since it is relatively stable, it is necessary to tighten the reaction conditions during chlorination, which causes an oxidation reaction of the raw material or target product, resulting in an increase in by-products. For this reason, when producing dichlorophenols by chlorination of phenols,
It is desired to develop a method for producing dichlorophenols at low cost, in good yield, safely, and easily from an industrial standpoint. Means for Solving the Problems The present invention was achieved as a result of extensive research into methods for producing dichlorophenols, particularly p-substituted dichlorophenols, which are free from the above-mentioned problems. That is, the present invention provides formula (1) (In formula (1), R 1 represents halogen, C 1 to 4 alkyl, nitro, or carboxyl, and R 2 represents hydrogen, sodium, potassium, or lithium.) in the presence
Formula (2) characterized by reacting hypochlorous acid or/and its salt at PH2.0 to 7.0 (In formula (2), R 1 has the same meaning as above)
The present invention provides a method for producing dichlorophenols represented by: The method of the present invention will be explained in detail. In the method of the present invention, water is used as a reaction medium, and the amount used is 2 to 10 times, preferably 3 to 5 times (weight ratio), relative to the p-substituted phenols used as raw materials. In addition, for the purpose of lowering the viscosity of the reaction solution, up to 20% (volume) of a halogenated aliphatic hydrocarbon such as dichloromethane or tetrachloroethane can be added to the water. As the dispersant used in the method of the present invention, a nonionic, cationic or anionic dispersant is used, and specific examples thereof include POE (polyoxyethylene) lauryl ether, POE higher alcohol ether, POE octyl ether, enyl ether, POE nonyl phenyl ether, ethylenediamine POE/POP (polyoxypropylene)
POE or POP derivatives such as condensates, quaternary ammonium salts such as cetyltrimethylammonium chloride, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, alkylmethyltauride, formalinnaphthalene sulfonic acid Examples include condensates of. The above-mentioned dispersant is used in the amount of the reaction liquid, and if necessary, 0.01% to 10% (weight/volume), preferably 0.1%.
% to 3% (weight/volume) is used. Specific examples of Lewis acids used in the present invention include ferric chloride,
Examples include aluminum chloride, zinc chloride, magnesium chloride, tin chloride, etc., but from the viewpoint of handling and cost, it is preferable to use ferric chloride and aluminum chloride. The amount used is 0.01 to 0.01 to the reaction substrate.
It is preferably 20 mol%, more preferably 0.1 to 10 mol%. In the method of the present invention, both the above-mentioned dispersant and Lewis acid may be used, or only one of them may be used. p- used as raw material in the method of the present invention
Specific examples of substituted phenols include the following:
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】
が挙げられこれらはそのナトリウム、カリウム又
はリチウム塩であつてもよい。
本発明においてクロル化剤として働く次亜塩素
酸又は／及びその塩としては、次亜塩素酸又はそ
のナトリウム塩、カリウム塩等のアルカリ金属塩
が用いられるがそれらの混合物を用いてもよい。
その使用量はｐ−置換フエノール類に対し理論量
の90〜150モル％であり、好ましくは100〜130モ
ル％である。
本発明の方法では、前記したようなｐ−置換フ
エノール類を水に加え前記した分散剤及び／又は
ルイス酸を加え攪拌下、５〜70℃好ましくは10〜
30℃でクロル化剤を１〜10時間、好ましくは４〜
８時間かけて滴下する。滴下終了と同時に反応は
終了するが必要に応じ更に１〜２時間の範囲で攪
拌を続けてもよい。この間反応液をPH＝２〜７、
特に好ましくは３〜６に制禦する必要がある。PH
が２未満であるとポリハロゲン化（ベンゼン核に
塩素が３個以上入つた化合物を生成）をおこし又
PHが７をこすと反応基質及び生成物の酸化反応が
おこり共に目的化合物の純度、収率低下をきた
す。
このPHの制禦には酸又はアルカリを使用する。
酸としては塩酸、硫酸、硝酸、リン酸等の無機酸
及び蟻酸、酢酸、ピロピオン酸等の有機酸が用い
られ又無機酸、有機酸の混合物であつてもさしつ
かえない。アルカリとしては、アルカリ金属水酸
化物、アルカリ金属炭酸塩、アルカリ金属酢酸塩
等が挙げられ、これらは通常それらの水溶液にし
て加えられその濃度は、反応液が所定のPHに維持
できるものであれば、特に制限はない。
反応終了後は反応液重量に対して10〜20％（重
量）の無機塩（例えば食塩、硫酸ナトリウム）を
加えて沈澱を別してもよいし又反応液に酸を加
えてフリーのｐ−置換ジクロロフエノールを別
してもよい。なお前者においては用いる原料によ
つてフリーのｐ−置換ジクロロフエノールあるい
はこれとそのナトリウム、カリウム又はリチウム
塩の混合物として目的物がえられる。又反応液に
酸を加えたあとトルエン・クロルベンゼン、キシ
レン等の有機溶媒によつて抽出して目的物をえて
もよい。
こうしてえられたｐ−置換ジクロロフエノール
（又はそのナトリウム、カリウム又はリチウム塩）
は高純度であるのでそのまま医・農薬、染・顔料
の原料として使用することが出来るが、さらに高
純度が必要な場合には再結晶法等によつて精製す
ることも出来る。
又反応液から目的物を分離することなく反応が
終了した反応液をそのまま次の反応工程に使用す
ることも出来る。
本発明の方法によると設備費のかさむ高価な反
応装置を必要とせず安価な原料によりしかも高純
度、高収率でｐ−置換ジクロロフエノール（又は
そのナトリウム、カリウム又はリチウム塩）類を
えることが出来る。
実施例
本発明を実施例によつて更に詳細に説明する。
実施例 １
攪拌機、温度計、滴下ロ斗を備えた200mlビー
カーに水35ml、ｐ−ニトロフエノールのナトリウ
ム塩10ｇ、デモールＮ（分散剤、ナフタリンスル
ホン酸のホルマリン縮合物、花王(株)製）0.2ｇと
塩化第２鉄0.1ｇを仕込み氷水浴中で冷却しなが
ら攪拌し続いてPH計を装着後、濃塩酸にてPH＝５
とした。次いで15.5％（容量％）次亜塩素酸ナト
リウム水溶液を６時間を要して59ml滴下した。こ
の間、反応温度は10〜15℃に保ち、同時にPH＝
5.0±0.2となる様、濃塩酸を適宜滴下した。
滴下終了後、同温度で30分攪拌を続けた後濃塩
酸を加え、PH＝１とし生成した黄白色の結晶を
別した。乾燥した生成物
（[Formula] and these may be their sodium, potassium or lithium salts. In the present invention, hypochlorous acid or alkali metal salts thereof such as sodium salts and potassium salts are used as hypochlorous acid and/or its salts which act as chlorinating agents, but mixtures thereof may also be used.
The amount used is 90 to 150 mol%, preferably 100 to 130 mol% of the theoretical amount based on the p-substituted phenol. In the method of the present invention, the above-mentioned p-substituted phenols are added to water, the above-mentioned dispersant and/or Lewis acid are added, and the mixture is heated at 5-70°C, preferably at 10-70°C.
Chlorinating agent at 30℃ for 1-10 hours, preferably 4-10 hours.
Drip over 8 hours. The reaction ends at the same time as the addition ends, but stirring may be continued for an additional 1 to 2 hours if necessary. During this time, the reaction solution was adjusted to pH=2-7.
Particularly preferably, it is necessary to limit the number to 3 to 6. PH
If it is less than 2, polyhalogenation (forming a compound with three or more chlorine atoms in the benzene nucleus) may occur.
When the pH exceeds 7, an oxidation reaction of the reaction substrate and product occurs, resulting in a decrease in the purity and yield of the target compound. Acid or alkali is used to control this pH.
As the acid, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as formic acid, acetic acid, and pyropionic acid are used, and mixtures of inorganic acids and organic acids may also be used. Examples of the alkali include alkali metal hydroxides, alkali metal carbonates, alkali metal acetates, etc. These are usually added in the form of aqueous solutions, and the concentration is such that the reaction solution can be maintained at a predetermined pH. There are no particular restrictions. After the reaction is complete, 10 to 20% (by weight) of an inorganic salt (e.g., common salt, sodium sulfate) based on the weight of the reaction solution may be added to separate the precipitate, or an acid may be added to the reaction solution to remove free p-substituted dichloromethane. Phenol may be separated. In the above method, depending on the raw materials used, the desired product can be obtained as free p-substituted dichlorophenol or a mixture of this and its sodium, potassium or lithium salts. Alternatively, the desired product may be obtained by adding an acid to the reaction solution and then extracting with an organic solvent such as toluene, chlorobenzene or xylene. p-substituted dichlorophenol (or its sodium, potassium or lithium salt) thus obtained
Because of its high purity, it can be used as it is as a raw material for medicines, agricultural chemicals, dyes, and pigments, but if even higher purity is required, it can be purified by recrystallization. Further, the reaction solution after the reaction can be used as it is in the next reaction step without separating the target product from the reaction solution. According to the method of the present invention, p-substituted dichlorophenols (or their sodium, potassium or lithium salts) can be obtained with high purity and high yield using inexpensive raw materials without the need for expensive reaction equipment with high equipment costs. I can do it. EXAMPLES The present invention will be explained in more detail by way of examples. Example 1 In a 200 ml beaker equipped with a stirrer, thermometer, and dropping funnel, 35 ml of water, 10 g of sodium salt of p-nitrophenol, and 0.2 Demol N (dispersant, formalin condensate of naphthalene sulfonic acid, manufactured by Kao Corporation) were added. g and 0.1 g of ferric chloride, stirred while cooling in an ice water bath, and after installing a PH meter, adjusted the pH to 5 with concentrated hydrochloric acid.
And so. Next, 59 ml of a 15.5% (volume %) aqueous sodium hypochlorite solution was added dropwise over a period of 6 hours. During this time, the reaction temperature was kept at 10-15℃, and at the same time PH=
Concentrated hydrochloric acid was appropriately added dropwise so that the ratio was 5.0±0.2. After the addition was completed, stirring was continued for 30 minutes at the same temperature, and then concentrated hydrochloric acid was added to adjust the pH to 1, and the yellowish white crystals formed were separated. Dry product (
【式】）の純度は、98.1％
（HSLC）であり、少量のモノクロル体を含む以
外副生物は極めて微量であつた。得られた２，６
−ジクロロ−ｐ−ニトロフエノールの融点は122
〜124℃（分解）を示し、収量は、10.0ｇで、こ
れは理論値の95.0％の収率に相当する。
実施例 ２
実施例１と同様な操作にて、原料にｐ−ニトロ
フエノール（フリー）10ｇを用いたところ、２，
６−ジクロロ−ｐ−ニトロフエノールの14.1ｇが
えられ、これは理論量の94.2％に相当しその融点
は122〜124℃（分解）を示した。又純度は98.3％
（HSLC）であつた。
比較例 １
実施例１と同様な操作にて、デモールＮ及び塩
化第２鉄を無添加の状態で反応したところ、収量
86ｇで粗生成物をえたがこのものはモノクロル−
ｐ−ニトロフエノール11％、ｐ−ニトロフエノー
ル5.9％（HPLC）を含有していた。（目的物収率
67.7％）
比較例 ２
実施例１と同様な操作にて、反応液のPHを9.0
±0.2にコントロールして反応を実施したところ、
収量8.9ｇで粗生成物をえたがこのものはモノク
ロロ−ｐ−ニトロフエノール4.1％、トリクロロ
フエノール（脱NO2体）4.3％を含有していた
（HSLC分析による）。
比較例 ３
比較例２と同様にして反応液をPH＝0.5にコン
トロールして反応を実施したところ、収量8.5ｇ
で粗生成物をえたがこのものはモノクロロ−ｐ−
ニトロフエノール8.3％、不明不純物3.7％を含有
していた（HSLC分析による）。又原料を消滅せ
しめるのに要した次亜塩素酸ナトリウムの量はｐ
−ニトロフエノールに対し理論量の185モル％で
あつた。
実施例３〜９、比較例４〜６
実施例１に準じて表−１に示す条件下で反応を
実施した結果を表にまとめて示した。The purity of [Formula]) was 98.1% (HSLC), and there were very few by-products other than a small amount of monochloride. Obtained 2,6
-The melting point of dichloro-p-nitrophenol is 122
˜124° C. (decomposition) and the yield was 10.0 g, corresponding to a yield of 95.0% of theory. Example 2 In the same operation as in Example 1, using 10 g of p-nitrophenol (free) as the raw material, 2,
14.1 g of 6-dichloro-p-nitrophenol were obtained, corresponding to 94.2% of theory and having a melting point of 122 DEG -124 DEG C. (decomposition). Also, the purity is 98.3%
(HSLC). Comparative Example 1 When Demol N and ferric chloride were reacted without additives in the same manner as in Example 1, the yield was
86g of crude product was obtained, which was monochloro-
It contained 11% p-nitrophenol and 5.9% p-nitrophenol (HPLC). (Yield of target product
67.7%) Comparative Example 2 Using the same procedure as in Example 1, the pH of the reaction solution was adjusted to 9.0.
When the reaction was controlled to ±0.2,
A crude product was obtained in a yield of 8.9 g, containing 4.1% monochloro-p-nitrophenol and 4.3% trichlorophenol ( deNO2 ) (according to HSLC analysis). Comparative Example 3 The reaction was carried out in the same manner as Comparative Example 2 by controlling the reaction solution to PH = 0.5, and the yield was 8.5 g.
A crude product was obtained, which was monochloro-p-
Contained 8.3% nitrophenol and 3.7% unknown impurities (according to HSLC analysis). Also, the amount of sodium hypochlorite required to eliminate the raw material is p
- 185 mol % of theory based on nitrophenol. Examples 3 to 9, Comparative Examples 4 to 6 According to Example 1, reactions were carried out under the conditions shown in Table 1. The results are summarized in a table.
【表】【table】
【表】
ムクロライドをそれぞれ示す。
(2) 実施例3〜6は反応終了後トルエン50ml
にて3回抽出して目的物を得た。
発明の効果
ｐ−置換フエノール類のクロル化によるジクロ
ロフエノール類を製造するにあたり、安価に、収
率よく安全でそして工業的に容易な生産設備に
て、ジクロロフエノール類が製造できるようにな
つた。[Table] Shows each muchloride.
(2) For Examples 3 to 6, 50 ml of toluene was added after the reaction was completed.
The target product was obtained by extraction three times.
Effects of the Invention In producing dichlorophenols by chlorination of p-substituted phenols, it has become possible to produce dichlorophenols at low cost, with good yield, using safe and industrially easy production equipment.
Claims (1)
キル、ニトロ又はカルボキシルを、R2は水素、
ナトリウム、カリウム又はリチウムを表す）で表
される化合物に分散剤又は／及びルイス酸の存在
下、PH＝２〜７で次亜塩素酸又は／及びその塩を
作用させる事を特長とする式(2) （式(2)において、R1は前記と同じ意味を表す）
で表されるジクロロフエノール類の製造法。[Claims] 1 Formula (1) (In formula (1), R 1 is halogen, C 1-4 alkyl, nitro or carboxyl, R 2 is hydrogen,
A formula (representing sodium, potassium or lithium) characterized by the action of hypochlorous acid or/and its salt in the presence of a dispersant or/and a Lewis acid at pH=2 to 7. 2) (In formula (2), R 1 has the same meaning as above)
A method for producing dichlorophenols represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1376886A JPS62175429A (en) | 1986-01-27 | 1986-01-27 | Production of dichlorophenol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1376886A JPS62175429A (en) | 1986-01-27 | 1986-01-27 | Production of dichlorophenol compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62175429A JPS62175429A (en) | 1987-08-01 |
| JPH0551569B2 true JPH0551569B2 (en) | 1993-08-03 |
Family
ID=11842429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1376886A Granted JPS62175429A (en) | 1986-01-27 | 1986-01-27 | Production of dichlorophenol compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62175429A (en) |
-
1986
- 1986-01-27 JP JP1376886A patent/JPS62175429A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62175429A (en) | 1987-08-01 |
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