JPH0232048A - Production of halophenoxyamines - Google Patents
Production of halophenoxyaminesInfo
- Publication number
- JPH0232048A JPH0232048A JP17875088A JP17875088A JPH0232048A JP H0232048 A JPH0232048 A JP H0232048A JP 17875088 A JP17875088 A JP 17875088A JP 17875088 A JP17875088 A JP 17875088A JP H0232048 A JPH0232048 A JP H0232048A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- sodium salt
- hydroxylamine
- sulfonic acid
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 29
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- DQPBABKTKYNPMH-UHFFFAOYSA-N amino hydrogen sulfate Chemical compound NOS(O)(=O)=O DQPBABKTKYNPMH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 abstract description 32
- 239000002994 raw material Substances 0.000 abstract description 4
- 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 abstract description 2
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- PCSYDOORDVYWPI-UHFFFAOYSA-N o-(3,5-dichlorophenyl)hydroxylamine Chemical compound NOC1=CC(Cl)=CC(Cl)=C1 PCSYDOORDVYWPI-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000011734 sodium Substances 0.000 abstract description 2
- 229910052708 sodium Inorganic materials 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- VPOMSPZBQMDLTM-UHFFFAOYSA-N 3,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC(Cl)=C1 VPOMSPZBQMDLTM-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- -1 hydroxyl- Chemical group 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- SZNYYWIUQFZLLT-UHFFFAOYSA-N 2-methyl-1-(2-methylpropoxy)propane Chemical compound CC(C)COCC(C)C SZNYYWIUQFZLLT-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- IJGSULQFKYOYEU-UHFFFAOYSA-N 2,3,4-trifluorophenol Chemical compound OC1=CC=C(F)C(F)=C1F IJGSULQFKYOYEU-UHFFFAOYSA-N 0.000 description 1
- FNAKEOXYWBWIRT-UHFFFAOYSA-N 2,3-dibromophenol Chemical compound OC1=CC=CC(Br)=C1Br FNAKEOXYWBWIRT-UHFFFAOYSA-N 0.000 description 1
- UMPSXRYVXUPCOS-UHFFFAOYSA-N 2,3-dichlorophenol Chemical compound OC1=CC=CC(Cl)=C1Cl UMPSXRYVXUPCOS-UHFFFAOYSA-N 0.000 description 1
- RPEPGIOVXBBUMJ-UHFFFAOYSA-N 2,3-difluorophenol Chemical compound OC1=CC=CC(F)=C1F RPEPGIOVXBBUMJ-UHFFFAOYSA-N 0.000 description 1
- BSWWXRFVMJHFBN-UHFFFAOYSA-N 2,4,6-tribromophenol Chemical compound OC1=C(Br)C=C(Br)C=C1Br BSWWXRFVMJHFBN-UHFFFAOYSA-N 0.000 description 1
- RANCECPPZPIPNO-UHFFFAOYSA-N 2,5-dichlorophenol Chemical compound OC1=CC(Cl)=CC=C1Cl RANCECPPZPIPNO-UHFFFAOYSA-N 0.000 description 1
- GNWKBOXWJIRYCL-UHFFFAOYSA-N 2-bromo-3,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Br GNWKBOXWJIRYCL-UHFFFAOYSA-N 0.000 description 1
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 1
- KQDJTBPASNJQFQ-UHFFFAOYSA-N 2-iodophenol Chemical compound OC1=CC=CC=C1I KQDJTBPASNJQFQ-UHFFFAOYSA-N 0.000 description 1
- PYNATBPUJOURNL-UHFFFAOYSA-N 3,4-dichloro-2-fluorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1F PYNATBPUJOURNL-UHFFFAOYSA-N 0.000 description 1
- DUKKNDLIWRYBCT-UHFFFAOYSA-N 3-bromo-2-chlorophenol Chemical compound OC1=CC=CC(Br)=C1Cl DUKKNDLIWRYBCT-UHFFFAOYSA-N 0.000 description 1
- PCHPYNHSMSAJEU-UHFFFAOYSA-N 3-chloro-2-fluorophenol Chemical compound OC1=CC=CC(Cl)=C1F PCHPYNHSMSAJEU-UHFFFAOYSA-N 0.000 description 1
- SJTBRFHBXDZMPS-UHFFFAOYSA-N 3-fluorophenol Chemical compound OC1=CC=CC(F)=C1 SJTBRFHBXDZMPS-UHFFFAOYSA-N 0.000 description 1
- HVLUXBQZVNQLTE-UHFFFAOYSA-N 4-chloro-2,3-difluorophenol Chemical compound ClC1=C(C(=C(C=C1)O)F)F HVLUXBQZVNQLTE-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UOKZUTXLHRTLFH-UHFFFAOYSA-N o-phenylhydroxylamine Chemical class NOC1=CC=CC=C1 UOKZUTXLHRTLFH-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
童栗上■剋里分立
本発明は、医薬品、農薬等の製造における中間原料とし
て有用であるハロフェノキシアミン類の製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing halophenoxyamines, which are useful as intermediate raw materials in the production of pharmaceuticals, agricultural chemicals, and the like.
従来少狭歪
ハロフェノキシアミン類の製造方法として、従来、式（
１）に示すように、ハロフェノール類のカリウム塩にヒ
ドロキシル−〇−アミンスルホン酸を反応させる方法が
知られている（ケミストリー・アンド・インダストリー
（Ｃｈｅｍｉｓｔｒｙ ＆ Ｉｎｄｕｓｔｒｙ）５５９
頁、１９６２年や、ジャーナル・オフ・ザ・ケミカル・
ソサイエテイ、パーキン・トランザクションズＩ （
Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ｃｈｅｍｉｃａｌ ５
ｏｃｉｅｔｙ。Conventionally, as a manufacturing method for narrowly strained halophenoxyamines, the formula (
As shown in 1), a method is known in which potassium salts of halophenols are reacted with hydroxyl-〇-aminesulfonic acid (Chemistry & Industry 559).
Page, 1962, Journal of the Chemical
Society, Perkin Transactions I (
Journal of the Chemical 5
ocity.
Ｐｅｒｋｉｎ Ｔｒａｎｓａｃｔｉｏｎｓ Ｉ ）
、１８２７頁、１９７７年）。Perkin Transactions I)
, p. 1827, 1977).
Ｘｎ 上式において、Ｘはハロゲン原子を示す。Xn In the above formula, X represents a halogen atom.
しかし、この方法は、高価なカリウム塩を使用すると共
に、目的とするハロフェノキシアミン類の収率も精々約
１５％と極めて低く、実用的ではない。However, this method uses expensive potassium salts and the yield of the desired halophenoxyamines is extremely low, at most about 15%, and is not practical.
そこで、本発明者らは、上記の方法において、フェノキ
シアミン類の収率の向上を図ることを目的として鋭意研
究した結果、特開昭６１−１３７８４２号公報に記載さ
れているように、反応系に硫酸塩、金属キレート剤、オ
レフィン類又はニトロフェノール類を存在させることに
よって、上記目的を達成することができ、ハロフェノキ
シアミン類の収率を最高約３５％まで高め得ることを見
出している。Therefore, as a result of intensive research aimed at improving the yield of phenoxyamines in the above method, the present inventors discovered that the reaction system It has been found that the above object can be achieved by the presence of sulfate, metal chelating agent, olefins or nitrophenols in the process, and the yield of halophenoxyamines can be increased up to about 35%.
が ゛ しようとする
本発明者らは、ハロフェノキシアミン類を一層工業的に
有利に、即ち、より高収率且つ経済的に製造するために
、更に鋭意研究を進めた結果、工業的に最も低度なハロ
フェノール類のナトリウム塩を用いると共に、これに所
定の条件下にヒドロキシルアミン−〇−スルホン酸を反
応させることによって、先に挙げた硫酸塩、金属キレー
ト剤、オレフィン類又はニトロフェノール類を必要とせ
ずして、ハロフェノキシアミン類を高収率且つ経済的に
製造することができることを見出して、本発明に至った
ものである。In order to produce halophenoxyamines more industrially, in other words, in a higher yield and more economically, the inventors of the present invention have carried out further intensive research, and as a result, they have developed the most industrially possible product. By using a sodium salt of a low-grade halophenol and reacting it with hydroxylamine-〇-sulfonic acid under specified conditions, the above-mentioned sulfates, metal chelating agents, olefins, or nitrophenols can be prepared. The present invention was achieved by discovering that halophenoxyamines can be produced economically in high yield without the need for.
シ を１するための
本発明によるハロフェノキシアミン類の製造方法は、−
数式
（式中、Ｘはハロゲン原子、ｎは１〜３の整数を示す。The method for producing halophenoxyamines according to the present invention for producing -
Numerical formula (wherein, X represents a halogen atom, and n represents an integer of 1 to 3.
）
で表わされるハロフェノール類のナトリウム塩の２〜８
モル／１水溶液に加熱下にヒドロキシルアミン−〇−ス
ルホン酸の０．５〜１０モル／１の水溶液を上記ハロフ
ェノール類のナトリウム塩１モルに対してヒドロキシル
アミン−〇−スルホン酸が０．１〜０．４モルの割合に
なるように加え、反応させることによって、−数式（Ｉ
Ｉ）
Ｘｎ
（式中、Ｘ及びｎは前記と同じである。）で表わされる
ハロフェノキシアミン類を得るものである。) 2-8 of sodium salts of halophenols represented by
A 0.5 to 10 mole/1 aqueous solution of hydroxylamine-〇-sulfonic acid is added to a mol/1 aqueous solution while heating. - Formula (I
I) Halophenoxyamines represented by Xn (wherein X and n are the same as above) are obtained.
以下に本発明の方法について詳細に説明する。The method of the present invention will be explained in detail below.
本発明の方法において、原料として用いるハロフェノー
ル類のナトリウム塩は、前記−数式（１）で表わされ、
前記ハロゲン原子は、フッ素、塩素、臭素又はヨウ素で
ある。ハロフェノール類のナトリウム塩が２以上のハロ
ゲン原子を有するときは、これらハロゲン原子は相互に
同じでも、異なっていてもよい。In the method of the present invention, the sodium salt of halophenols used as a raw material is represented by the above formula (1),
The halogen atom is fluorine, chlorine, bromine or iodine. When the sodium salt of halophenols has two or more halogen atoms, these halogen atoms may be the same or different.
従って、かかるハロフェノール類の具体例として、例え
ば、フルオロフェノール、ジフルオロフェノール、トリ
フルオロフェノール、クロロフェノール、ジクロロフェ
ノール、トリクロロフェノール、ブロモフェノール、ジ
ブロモフェノール、トリブロモフェノール、ヨードフェ
ノール、ショートフェノール、クロロフルオロフェノー
ル、ジクロロフルオロフェノール、クロロジフルオロフ
ェノール、ブロモクロロフェノール、ブロモジクロロフ
ェノール等を挙げることができる。Therefore, specific examples of such halophenols include fluorophenol, difluorophenol, trifluorophenol, chlorophenol, dichlorophenol, trichlorophenol, bromophenol, dibromophenol, tribromophenol, iodophenol, shortphenol, chlorofluorophenol, etc. Examples include phenol, dichlorofluorophenol, chlorodifluorophenol, bromochlorophenol, bromodichlorophenol, and the like.
前記−数式（１）で表わされるハロフェノール類のナト
リウム塩は、既に知られているように、対応するハロフ
ェノール類に水酸化ナトリウムを水溶液中で反応させる
ことによって得ることができる。ハロフェノール類のナ
トリウム塩は、上記反応系から単離して、本発明による
反応に用いてもよく、或いは単離することなく、これを
含む上記水溶液をそのまま、本発明による反応に用いて
もよい。As is already known, the sodium salt of the halophenol represented by formula (1) can be obtained by reacting the corresponding halophenol with sodium hydroxide in an aqueous solution. The sodium salt of halophenols may be isolated from the above reaction system and used in the reaction according to the present invention, or the above aqueous solution containing it may be used as it is in the reaction according to the present invention without being isolated. .
本発明の方法によれば、ハロフェノール類のナトリウム
塩の水溶液にヒドロキシルアミン−〇−スルホン酸の水
溶液を加え、反応させることによつて、ハロフェノキシ
アミン類を得る。ここに、反応に用いるハロフェノール
類のナトリウム塩の水溶液の濃度は、目的とするハロフ
ェノキシアミン類を高収率にて得るために極めて重要な
因子の一つであって、本発明の方法においては、濃度２
〜８モル／ｌの水溶液が用いられる。特に、濃度３〜６
モル／１の水溶液が好ましく用いられる。According to the method of the present invention, halophenoxyamines are obtained by adding an aqueous solution of hydroxylamine-〇-sulfonic acid to an aqueous solution of a sodium salt of a halophenol and causing a reaction. Here, the concentration of the aqueous solution of the sodium salt of halophenols used in the reaction is one of the extremely important factors in order to obtain the desired halophenoxyamines in high yield, and in the method of the present invention. is concentration 2
~8 mol/l aqueous solution is used. In particular, concentration 3-6
A mol/1 aqueous solution is preferably used.
ハロフェノール類のナトリウム塩の水溶液の濃度が上記
範囲にないときは、目的とするハロフェノキシアミン類
の収率が著しく低い。When the concentration of the aqueous solution of the sodium salt of halophenols is not within the above range, the yield of the desired halophenoxyamines is extremely low.
更に、本発明によれば、ヒドロキシルアミン−〇−スル
ホン酸は、濃度０．５〜１０モル／Ｉｌの水溶液として
、ハロフェノール類のナトリウム塩１モルに対して、０
．１〜０．４１モル、好ましくは０．１５〜０．３５モ
ルの割合にて、ハロフェノール類のナトリウム塩の水溶
液に加熱撹拌下に加えられる。Furthermore, according to the present invention, hydroxylamine-〇-sulfonic acid, as an aqueous solution with a concentration of 0.5 to 10 mol/Il, is used in an amount of 0 per mol of sodium salt of halophenols.
．． It is added to the aqueous solution of the sodium salt of halophenols at a ratio of 1 to 0.41 mol, preferably 0.15 to 0.35 mol, while stirring while heating.
これら条件も、前記ハロフェノール類のナトリウム塩の
水溶液の濃度と同様に、本発明に従って、高収率にてハ
ロフェノキシアミン類を得るために重要な別の因子であ
る。ヒドロキシルアミン−Ｏ−スルホン酸水溶液の添加
時間は、特に限定されるものではないが、通常、０．１
〜２時間、好ましくは０．２〜１時間である。These conditions, as well as the concentration of the aqueous solution of the sodium salt of halophenols, are other important factors for obtaining halophenoxyamines in high yield according to the present invention. The addition time of the hydroxylamine-O-sulfonic acid aqueous solution is not particularly limited, but is usually 0.1
-2 hours, preferably 0.2-1 hour.
ヒドロキシルアミン−〇−スルホン酸水溶液ヲハロフェ
ノール類のナトリウム塩水溶液に加エルに際しては、前
述したように、ハロフェノール類のナトリウム塩水溶液
は、加熱下に撹拌される。When adding the aqueous solution of hydroxylamine-〇-sulfonic acid to the aqueous solution of sodium salt of halophenols, the aqueous solution of sodium salt of halophenols is stirred while heating, as described above.
加熱温度は、通常、６０〜１１０℃の範囲であり、好ま
しくは７０〜ｌＯＯ℃の範囲である。The heating temperature is usually in the range of 60 to 110°C, preferably in the range of 70 to 100°C.
本発明においては、ハロフェノール類のナトリウム塩の
水溶液にヒドロキシルアミン−〇−スルホン酸水溶液を
加えてもよいが、ハロフェノール類のナトリウム塩の水
溶液に水と混和しない有機溶剤を共存させて、これにヒ
ドロキシルアミンＯ−スルホン酸水溶液を加えるのが好
ましい。この後者の方法によれば、生成物であるハロフ
ェノキシアミンが有機溶剤中に移行し、反応が促進され
ると共に、反応終了後の後処理も容易である。In the present invention, an aqueous solution of hydroxylamine-〇-sulfonic acid may be added to an aqueous solution of a sodium salt of a halophenol; Preferably, an aqueous solution of hydroxylamine O-sulfonic acid is added to the solution. According to this latter method, the product halophenoxyamine is transferred into the organic solvent, the reaction is accelerated, and post-treatment after the completion of the reaction is also easy.
尚、このように、反応をハロフェノール類のナトリウム
塩の水溶液と有機溶剤との２相系で行なう場合も、ハロ
フェノール類のナトリウム塩の水溶液濃度とは、用いた
水におけるハロフェノール類のナトリウム塩の濃度とす
る。In this way, even when the reaction is carried out in a two-phase system consisting of an aqueous solution of the sodium salt of halophenols and an organic solvent, the concentration of the aqueous solution of the sodium salt of halophenols refers to the concentration of the sodium salt of halophenols in the water used. Let be the concentration of salt.
上記のように、２相系で反応を行なう場合に用いる有機
溶剤としては、例えば、ヘキサン、ヘプタン、オクタン
、ノナン、デカン、シクロヘキサン、メチルシクロヘキ
サン、灯油等の脂肪族炭化水素や脂環式炭化水素、ベン
ゼン、トルエン、キシレン、クメン等の芳香族炭化水素
、ジ−ｎ−プロピルエーテル、ジイソプロピルエーテル
、シーｎ−ブチルエーテル、ジイソブチルエーテル、ア
ニソール等の脂肪族エーテルや芳香族エーテルを挙げる
ことができる。As mentioned above, examples of organic solvents used when carrying out the reaction in a two-phase system include aliphatic hydrocarbons and alicyclic hydrocarbons such as hexane, heptane, octane, nonane, decane, cyclohexane, methylcyclohexane, and kerosene. , aromatic hydrocarbons such as benzene, toluene, xylene, and cumene, and aliphatic ethers and aromatic ethers such as di-n-propyl ether, diisopropyl ether, sea-n-butyl ether, diisobutyl ether, and anisole.
前述したように、加熱撹拌下にハロフェノール類のナト
リウム類の水溶液にヒドロキシルアミン−０−スルホン
酸水溶液を加えた後、更に、撹拌加熱を続けてもよい。As described above, after adding the hydroxylamine-0-sulfonic acid aqueous solution to the aqueous solution of sodium halophenols while stirring with heating, stirring and heating may be continued.
かかる場合、その撹拌加熱の時間は、通常、０．１〜５
時間、好ましくは０．２〜２時間である。しかし、この
撹拌加熱は、必ずしも必要ではない。In such a case, the stirring and heating time is usually 0.1 to 5
time, preferably 0.2 to 2 hours. However, this stirring and heating is not always necessary.
反応終了後、前記−数式で表わされるハロフェノキシア
ミン類を単離するには、反応混合物を室温まで冷却した
後、反応媒体として前記有機溶剤を用いて、反応を２相
系で行なった場合は、２層に分液後、有機層を分取し、
これをアルカリ水溶液で洗浄し、乾燥し、濃縮乾固すれ
ばよい。また、有機溶剤を用いることな（、反応を均一
な水溶液系で行なった場合は、反応終了後、反応混合物
にトルエン等の有機溶剤を加え、ハロフェノキシアミン
類を有機層に抽出した後、有機層を前記したように処理
することによって、ハロフェノキシアミン類を単離する
ことができる。After the completion of the reaction, in order to isolate the halophenoxyamine represented by the above formula, the reaction mixture is cooled to room temperature, and when the reaction is carried out in a two-phase system using the above organic solvent as the reaction medium, , after separating into two layers, separate the organic layer,
This may be washed with an aqueous alkaline solution, dried, and concentrated to dryness. In addition, without using an organic solvent (if the reaction is carried out in a homogeneous aqueous solution system, after the reaction is complete, add an organic solvent such as toluene to the reaction mixture, extract the halophenoxyamines to the organic layer, and then By treating the layer as described above, the halophenoxyamines can be isolated.
主班■須来
以上のように、本発明の方法によれば、ハロフェノール
類のナトリウム塩に所定条件下にヒドロキシルアミン−
〇−スルホン酸を反応させることによって、従来の方法
に比べて、区かに高収率に且つ経済的にハロフェノキシ
アミン類を得ることができる。Main Team: Sugu As mentioned above, according to the method of the present invention, hydroxylamine-
By reacting with 〇-sulfonic acid, halophenoxyamines can be obtained in a much higher yield and economically than in conventional methods.
去施■
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLE 2 The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
３．５−ジクロロフェノールのナトリウム塩７．４０ｇ
（４０ミリモル）、水９ｍ１（上記ナトリウム塩の水に
おける濃度は４．４モル／１である。）及びトルエン３
０ｍ１の混合物を８０℃に加熱し、撹拌しつつ、これに
ヒドロキシルアミン−〇−スルホン［１１，１３ｇ（１
，０ミリモル、ハロフェノール類のナトリウム塩１モル
に対して０．２５モル）を含有する水溶液３ｍ１（３，
３モル／１）を４５分を要して滴下した。この滴下終了
後、更に、８０℃にて３０分間、撹拌を続けた。Example 1 7.40 g of sodium salt of 3.5-dichlorophenol
(40 mmol), 9 ml of water (the concentration of the above sodium salt in water is 4.4 mol/1) and 3 ml of toluene.
0 ml of the mixture was heated to 80°C and, with stirring, hydroxylamine-〇-sulfone [11.13 g (1
, 0 mmol, 0.25 mol per mol of sodium salt of halophenols).
3 mol/1) was added dropwise over 45 minutes. After this dropwise addition was completed, stirring was further continued at 80° C. for 30 minutes.
反応終了後、反応混合物を室温まで冷却し、分離したト
ルエン層を５％水酸化ナトリウム水溶液、水、次いで、
飽和食塩水にて洗浄した後、無水硫酸マグネシウム上で
乾燥し、次いで、トルエンを留去することによって、３
，５−ジクロロフェノキシアミンｏ、 ｓ ｏ ｇを得
た。収率は４５％（ヒドロキシルアミン−〇−スルホン
酸を基準、以下、同じ。）であった。After the reaction was completed, the reaction mixture was cooled to room temperature, and the separated toluene layer was mixed with a 5% aqueous sodium hydroxide solution, water, and then
After washing with saturated brine, drying over anhydrous magnesium sulfate, and then distilling off toluene, 3
,5-dichlorophenoxyamine o,sog was obtained. The yield was 45% (based on hydroxylamine-〇-sulfonic acid, the same applies hereinafter).
実施例２〜７
実施例１において、用いた３、５−ジクロロフェノール
のナトリウム塩の量、及びこれを溶解させるために用い
た水の量を第１表に示すように変えた以外は、実施例１
と同様にして、反応を行なった。結果を第１表に示す。Examples 2 to 7 The same procedure was carried out as in Example 1, except that the amount of sodium salt of 3,5-dichlorophenol used and the amount of water used to dissolve it were changed as shown in Table 1. Example 1
The reaction was carried out in the same manner. The results are shown in Table 1.
実施例８
実施例１において、３，５−ジクロロフェノールのナト
リウム塩に代えて、２，５−ジクロロフェノールのナト
リウム塩を用いた以外は、実施例１と同様にして、反応
を行なった。対応するハロフェノキシアミンの収率は４
４％であった。Example 8 The reaction was carried out in the same manner as in Example 1, except that the sodium salt of 2,5-dichlorophenol was used instead of the sodium salt of 3,5-dichlorophenol. The yield of the corresponding halophenoxyamine is 4
It was 4%.
実施例９
実施例１において、３．５−ジクロロフェノールのナト
リウム塩に代えて、４−クロロフェノールのナトリウム
塩を用いた以外は、実施例１と同様にして、反応を行な
った。対応するハロフェノキシアミンの収率は４５％で
あった。Example 9 The reaction was carried out in the same manner as in Example 1, except that the sodium salt of 4-chlorophenol was used instead of the sodium salt of 3,5-dichlorophenol. The yield of the corresponding halophenoxyamine was 45%.
実施例１０
実施例１において、３．５−ジクロロフェノールのナト
リウム塩に代えて、３−フルオロフェノールのナトリウ
ム塩を用いた以外は、実施例１と同様にして、反応を行
なった。対応するハロフェノキシアミンの収率は４１％
であった。Example 10 The reaction was carried out in the same manner as in Example 1, except that the sodium salt of 3-fluorophenol was used instead of the sodium salt of 3.5-dichlorophenol. The yield of the corresponding halophenoxyamine is 41%
Met.
比較例１
実施例１において、３，５−ジクロロフェノールのナト
リウム塩に代えて、３．５−ジクロロフェノールのカリ
ウム塩を用いた以外は、実施例１と同様にして反応を行
なった結果、３．５−ジクロロフェノキシアミンの収率
は２１％であった。Comparative Example 1 The reaction was carried out in the same manner as in Example 1, except that potassium salt of 3,5-dichlorophenol was used in place of the sodium salt of 3,5-dichlorophenol. The yield of .5-dichlorophenoxyamine was 21%.
比較例２及び３
実施例１において、用いた３、５−ジクロロフェノール
のナトリウム塩を溶解させるために用いた水の量を第１
表に示すように変えた以外は、実施例１と同様にして、
反応を行なった。結果を第１表に示す。Comparative Examples 2 and 3 In Example 1, the amount of water used to dissolve the sodium salt of 3,5-dichlorophenol used was
The same procedure as in Example 1 was carried out except for the changes shown in the table.
The reaction was carried out. The results are shown in Table 1.
Claims (1)
モル／ｌ水溶液に加熱下にヒドロキシルアミン−Ｏ−ス
ルホン酸の０．５〜１０モル／ｌの水溶液を上記ハロフ
エノール類のナトリウム塩１モルに対してヒドロキシル
アミン−Ｏ−スルホン酸が０．１〜０．４モルの割合に
なるように加え、反応させることを特徴とする一般式（
II） ▲数式、化学式、表等があります▼（II） （式中、Ｘ及びｎは前記と同じである。） で表わされるハロフエノキシアミン類の製造方法。(1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, X is a halogen atom, and n is an integer from 1 to 3.) 8
A 0.5 to 10 mol/l aqueous solution of hydroxylamine-O-sulfonic acid was added to a mol/l aqueous solution while heating. The general formula (
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In the formula, X and n are the same as above.) A method for producing halofenoxyamines.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17875088A JPH0232048A (en) | 1988-07-18 | 1988-07-18 | Production of halophenoxyamines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17875088A JPH0232048A (en) | 1988-07-18 | 1988-07-18 | Production of halophenoxyamines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0232048A true JPH0232048A (en) | 1990-02-01 |
Family
ID=16053935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17875088A Pending JPH0232048A (en) | 1988-07-18 | 1988-07-18 | Production of halophenoxyamines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0232048A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005023757A1 (en) * | 2003-08-29 | 2005-03-17 | Basf Aktiengesellschaft | Process for production of o-substituted hydroxylamines |
| JP2007161273A (en) * | 2005-12-12 | 2007-06-28 | Atox Co Ltd | Carrier for carrying devices into tank through manhole, and coating film inspecting apparatus for inspecting tank inner wall using the carrier |
| CN104529816A (en) * | 2014-12-10 | 2015-04-22 | 宁波欧迅化学新材料技术有限公司 | Method for synthesizing O-phenylhydroxylamine hydrochloride |
-
1988
- 1988-07-18 JP JP17875088A patent/JPH0232048A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005023757A1 (en) * | 2003-08-29 | 2005-03-17 | Basf Aktiengesellschaft | Process for production of o-substituted hydroxylamines |
| CN100364963C (en) * | 2003-08-29 | 2008-01-30 | 巴斯福股份公司 | Preparation of O-substituted hydroxylamines |
| JP2007161273A (en) * | 2005-12-12 | 2007-06-28 | Atox Co Ltd | Carrier for carrying devices into tank through manhole, and coating film inspecting apparatus for inspecting tank inner wall using the carrier |
| CN104529816A (en) * | 2014-12-10 | 2015-04-22 | 宁波欧迅化学新材料技术有限公司 | Method for synthesizing O-phenylhydroxylamine hydrochloride |
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