JPH043381B2 - - Google Patents
Info
- Publication number
- JPH043381B2 JPH043381B2 JP59024992A JP2499284A JPH043381B2 JP H043381 B2 JPH043381 B2 JP H043381B2 JP 59024992 A JP59024992 A JP 59024992A JP 2499284 A JP2499284 A JP 2499284A JP H043381 B2 JPH043381 B2 JP H043381B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- group
- general formula
- groups
- water
- 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
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003729 cation exchange resin Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- WJPCKOTWRFPMBS-UHFFFAOYSA-N n-phenoxynitramide Chemical class [O-][N+](=O)NOC1=CC=CC=C1 WJPCKOTWRFPMBS-UHFFFAOYSA-N 0.000 claims description 6
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- -1 dinitrophenyl groups Chemical group 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- YLACRFYIUQZNIV-UHFFFAOYSA-N o-(2,4-dinitrophenyl)hydroxylamine Chemical compound NOC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O YLACRFYIUQZNIV-UHFFFAOYSA-N 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 125000001894 2,4,6-trinitrophenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1[N+]([O-])=O)[N+]([O-])=O)[N+]([O-])=O 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- JDQDSEVNMTYMOC-UHFFFAOYSA-N 3-methylbenzenesulfonic acid Chemical compound CC1=CC=CC(S(O)(=O)=O)=C1 JDQDSEVNMTYMOC-UHFFFAOYSA-N 0.000 description 1
- RJWBTWIBUIGANW-UHFFFAOYSA-N 4-chlorobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(Cl)C=C1 RJWBTWIBUIGANW-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- MFSUKOCGNJOMDD-UHFFFAOYSA-N n-ethoxyacetamide Chemical compound CCONC(C)=O MFSUKOCGNJOMDD-UHFFFAOYSA-N 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
- 125000006501 nitrophenyl group Chemical group 0.000 description 1
- NZMGKBDXJNWMPA-UHFFFAOYSA-N o-(2,4,6-trinitrophenyl)hydroxylamine Chemical compound NOC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NZMGKBDXJNWMPA-UHFFFAOYSA-N 0.000 description 1
- OOHKBWPOLBTKMR-UHFFFAOYSA-N o-(4-nitrophenyl)hydroxylamine Chemical compound NOC1=CC=C([N+]([O-])=O)C=C1 OOHKBWPOLBTKMR-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は一般式（）、
（式中、Ｘは水素、ハロゲン、低級アルキル基
又はハロゲンで置換された低級アルキル基を示
し、（５−ｎ）個のＸはそれぞれ同一又は異なる
ものでもよく、ｎは１ないし３の整数を示す。以
下同様。）で表わされるニトロフエノキシアミン
類の製造方法に関する。
一般式（）で表わされるニトロフエノキシア
ミン類は、医薬等の合成に際し有用な化合物であ
る。より具体的には、Ｎ−アミノ体、Ｓ−アミノ
体、Ｐ−アミノ体あるいはＣ−アミノ体の合成の
際のアミノ化試薬として広汎に利用できるほか、
本出願人の出願に係る本出願と同日付特許出願
「ｏ−アリールヒドロキシルアミンの製造方法」
にも記載の如く、ｏ−アミノ体の合成にも応用で
あるものである。
一般式（）で表わされるニトロフエノキシア
ミン類のあるものの製法については、下記の如く
一般式（）′で表わされる化合物を過塩素酸で
加水分解する方法が特開昭49−95927に提案され
ている。
しかし、この従来法では爆発性を有する過塩素
酸を用いるため、工業的な規模での製造には不適
当であるという大きな欠点があつた。
本発明者らは、一般式（）で表わされる化合
物の安価かつ安全な工業的合成法を開発する目的
で鋭意研究を行つた結果、本発明を完成するに至
つた。
すなわち本発明は、一般式（）、
で表わされる化合物をスルホン酸基含有化合物お
よびスルホン酸基含有陽イオン交換樹脂、フツ化
水素酸および硝酸からなる群より選ばれる物質の
存在下で加水分解することを特徴とする一般式
（）、
で表わされるニトロフエノキシアミン類の製造法
に関する。
以下、本発明を詳細に説明する。
本発明で原料として用いる一般式（）、
の化合物において、R1およびR2で示される低級
アルキル基としては、たとえばメチル基、エチル
基、プロピル基などを挙げることができる。ま
た、ｘ、ｎとしては、
で表示すれば、例えばニトロフエニル基類、ジニ
トロフエニル基類、トリニトロフエニル基類、フ
ルオロニトロフエニル基類、クロロニトロフエニ
ル基類、ブロモニトロフエニル基類、トリフルオ
ロニトロフエニル基類、フルオロジニトロフエニ
ル基類、クロロジニトロフエニル基類、ブロモジ
ニトロフエニル基類、トリフルオロジニトロフエ
ニル基類、メチルニトロフエニル基類、ニトロト
リフルオロメチル基類等を挙げることができる。
前記一般式（）で表わされる化合物は、たとえ
ば、Helvetica Chimica Acta、46巻、2009頁
（1963年）記載の方法に従い、塩基の存在下、次
式の反応で容量に合成することができる。
本発明においては、目的化合物たる一般式
（）で表わされるニトロフエノキシアミン類は、
一般式（）で表わされる化合物をスルホン酸基
含有化合物等の存在下に加水分解することによつ
て得られる。
ここで用いるスルホン酸基含有化合物として
は、ベンゼンスルホン酸、ｏ−トルエンスルホン
酸、ｍ−トルエンスルホン酸、ｐ−トルエンスル
ホン酸、ｐ−クロロベンゼンスルホン酸、ナフタ
リンスルホン酸などの芳香族スルホン酸、硫酸、
フルオロスルホン酸、クロロスルホン酸、メタン
スルホン酸、エタンスルホン酸、トリフルオロメ
タンスルホン酸などを挙げることができる。また
スルホン酸基含有イオン交換樹脂としては、通常
架橋ポリスチレンやポリテトラフルオロエチレン
樹脂にスルホン酸基を導入したもので、例えば商
品名Amberlyst 15、Amberlite IR−120、
Amberlite 200、Dowex 50、AG50、
Dowex50W、AG50W、Zeokarb225、Diaion
SK1、Diaion SK102ないし116、NafionHなど
として販売されているものを用いることができ
る。これらのスルホン酸基含有化合物、スルホン
酸基含有陽イオン交換樹脂、フツ化水素酸および
硝酸は各１種類を単独で使用することができるほ
か、２種以上を併用してもよい。
スルホン酸基含有化合物、フツ化水素酸および
硝酸の使用量は、通常一般式（）の化合物１モ
ルに対し0.01ないし100モルであり、好ましくは
１ないし10モルである。また、スルホン酸基含有
陽イオン交換樹脂の使用量は、そのイオン交換容
量にもよるが、通常一般式（）の化合物１重量
部に対し0.1ないし10重量部であり、好ましくは
0.3ないし５重量部である。加水分解に必要な水
の使用量は、通常一般式（）の化合物１モルに
対し１ないし200モル、好ましくは１ないし50モ
ルである。
本発明においては、上記の如く水を用いるので
水以外に他の溶媒を使用しなくても行うことがで
きるが、溶媒を用いることが好ましい。この場合
の溶媒としては、メタノール、エタノールなどの
アルコール類、ジエチルエーテル、テトラヒドロ
フラン、ジオキサン、ジメトキシエタン、ジグリ
ムなどのエーテル類などが好ましい。これらの溶
媒の使用量は通常一般式（）の化合物１重量部
に対し１ないし100重量部、好ましくは２ないし
20重量部である。反応温度は通常−40ないし150
℃、好ましくは−10ないし80℃である。反応時間
は通常0.1ないし50時間、好ましくは0.5ないし20
時間である。反応後、目的物（）を得るには、
たとえば過あるいは溶媒抽出など通常用いられ
る一般的な分離手段を採用することができる。さ
らに必要に応じて再結晶するかあるいは水と混和
しない有機溶媒に溶解後、アルカリ水で洗浄する
ことによつてより高純度の（）を得ることがで
きる。
次に実施例により説明する。
実施例 １
Ｏ−（２，４−ジニトロフエニル）アセトヒド
ロキサム酸エチルエステル
The present invention is based on the general formula (), (In the formula, X represents hydrogen, a halogen, a lower alkyl group, or a halogen-substituted lower alkyl group, each of the (5-n) Xs may be the same or different, and n is an integer of 1 to 3. The present invention relates to a method for producing nitrophenoxyamines represented by the following formula (the same applies hereinafter). Nitrophenoxyamines represented by the general formula () are useful compounds in the synthesis of pharmaceuticals and the like. More specifically, it can be widely used as an amination reagent in the synthesis of N-amino, S-amino, P-amino, or C-amino forms, and
Patent application filed on the same date as this application filed by the applicant: “Method for producing o-arylhydroxylamine”
As described in , this method can also be applied to the synthesis of o-amino compounds. Regarding the production of some nitrophenoxyamines represented by the general formula (), a method of hydrolyzing the compound represented by the general formula ()' with perchloric acid as shown below was proposed in JP-A-49-95927. has been done. However, this conventional method has a major drawback in that it is unsuitable for production on an industrial scale because it uses explosive perchloric acid. The present inventors have completed the present invention as a result of intensive research aimed at developing an inexpensive and safe industrial synthesis method for the compound represented by the general formula (). That is, the present invention provides the general formula (), General formula () characterized in that a compound represented by is hydrolyzed in the presence of a substance selected from the group consisting of a sulfonic acid group-containing compound, a sulfonic acid group-containing cation exchange resin, hydrofluoric acid and nitric acid, This invention relates to a method for producing nitrophenoxyamines represented by The present invention will be explained in detail below. General formula () used as a raw material in the present invention, In the compound, examples of the lower alkyl group represented by R 1 and R 2 include a methyl group, an ethyl group, and a propyl group. Also, as x and n, For example, nitrophenyl groups, dinitrophenyl groups, trinitrophenyl groups, fluoronitrophenyl groups, chloronitrophenyl groups, bromonitrophenyl groups, trifluoronitrophenyl groups, fluorodinitro Examples include phenyl groups, chlorodinitrophenyl groups, bromodinitrophenyl groups, trifluorodinitrophenyl groups, methylnitrophenyl groups, nitrotrifluoromethyl groups, and the like.
The compound represented by the general formula () can be synthesized in a volume by the reaction of the following formula in the presence of a base, for example, according to the method described in Helvetica Chimica Acta, Vol. 46, p. 2009 (1963). In the present invention, the target compound, nitrophenoxyamines represented by the general formula (), is
It can be obtained by hydrolyzing a compound represented by the general formula () in the presence of a sulfonic acid group-containing compound or the like. Examples of the sulfonic acid group-containing compound used here include aromatic sulfonic acids such as benzenesulfonic acid, o-toluenesulfonic acid, m-toluenesulfonic acid, p-toluenesulfonic acid, p-chlorobenzenesulfonic acid, naphthalenesulfonic acid, and sulfuric acid. ,
Examples include fluorosulfonic acid, chlorosulfonic acid, methanesulfonic acid, ethanesulfonic acid, and trifluoromethanesulfonic acid. Sulfonic acid group-containing ion exchange resins are usually crosslinked polystyrene or polytetrafluoroethylene resins with sulfonic acid groups, such as Amberlyst 15, Amberlite IR-120,
Amberlite 200, Dowex 50, AG50,
Dowex50W, AG50W, Zeokarb225, Diaion
Those sold as SK1, Diaion SK102 to 116, NafionH, etc. can be used. Each of these sulfonic acid group-containing compounds, sulfonic acid group-containing cation exchange resins, hydrofluoric acid, and nitric acid may be used alone, or two or more types may be used in combination. The amount of the sulfonic acid group-containing compound, hydrofluoric acid and nitric acid used is usually 0.01 to 100 mol, preferably 1 to 10 mol, per 1 mol of the compound of general formula (). The amount of the sulfonic acid group-containing cation exchange resin used depends on its ion exchange capacity, but is usually 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, per 1 part by weight of the compound of general formula ().
0.3 to 5 parts by weight. The amount of water required for hydrolysis is usually 1 to 200 mol, preferably 1 to 50 mol, per 1 mol of the compound of general formula (). In the present invention, since water is used as described above, the present invention can be carried out without using any other solvent other than water, but it is preferable to use a solvent. Preferred solvents in this case include alcohols such as methanol and ethanol, and ethers such as diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, and diglyme. The amount of these solvents used is usually 1 to 100 parts by weight, preferably 2 to 100 parts by weight, per 1 part by weight of the compound of general formula ().
It is 20 parts by weight. Reaction temperature is usually -40 to 150
°C, preferably -10 to 80 °C. The reaction time is usually 0.1 to 50 hours, preferably 0.5 to 20 hours.
It's time. After the reaction, to obtain the target product (),
For example, commonly used separation means such as filtration or solvent extraction can be employed. Furthermore, higher purity () can be obtained by recrystallizing it if necessary or dissolving it in an organic solvent that is immiscible with water and washing it with alkaline water. Next, an example will be explained. Example 1 O-(2,4-dinitrophenyl)acetohydroxamic acid ethyl ester
【式】4.0ｇ（15
ミリモル）をメタノール50mlに懸濁させ、その中
に20℃で75％硫酸水溶液7.0（硫酸54ミリモル、水
97ミリモル）を滴下した。20℃で８時間撹拌後、
反応混合物を水100mlの中に投入し、析出物を
取した。その析出物を酢酸エチル100mlに溶かし、
５％水酸化ナトリウム水溶液、次いで飽和食塩水
で洗浄後、無水硫酸マグネシウムで乾燥した。酢
酸エチルを留去するとｏ−（２，４−ジニトロフ
エニル）ヒドロキシルアミンが2.8ｇ得られた
（収率93％）。
実施例 ２〜５
実施例１において硫酸水溶液の代りに表１の酸
54ミリモルおよび水54ミリモルを用い、24時間反
応を行つた。実施例１と同様に処理したところ、
Ｏ−（２，４−ジニトロフエニル）ヒドロキシル
アミンが表１の収率で得られた。[Formula] Suspend 4.0 g (15 mmol) in 50 ml of methanol, and add 7.0 g (54 mmol of sulfuric acid, water) of 75% aqueous sulfuric acid at 20℃.
97 mmol) was added dropwise. After stirring at 20℃ for 8 hours,
The reaction mixture was poured into 100 ml of water, and the precipitate was collected. Dissolve the precipitate in 100ml of ethyl acetate,
After washing with a 5% aqueous sodium hydroxide solution and then with saturated brine, it was dried over anhydrous magnesium sulfate. When ethyl acetate was distilled off, 2.8 g of o-(2,4-dinitrophenyl)hydroxylamine was obtained (yield 93%). Examples 2 to 5 In Example 1, the acids in Table 1 were used instead of the sulfuric acid aqueous solution.
The reaction was carried out for 24 hours using 54 mmol and 54 mmol of water. When treated in the same manner as in Example 1,
O-(2,4-dinitrophenyl)hydroxylamine was obtained in the yield shown in Table 1.
【表】
実施例 ６
Ｏ−（２，４−ジニトロフエニル）アセトヒド
ロキサム酸エチルエステル4.0ｇ（15ミリモル）
をジオキサン50mlに溶かしたのち、陽イオン交換
樹脂（商品名Amberlyst15）13.5ｇおよび水1.7ｇ
を加え、80℃で６時間撹拌した。室温まで冷却
後、陽イオン交換樹脂を過し、液を水100ml
の中に投入した。次に５％水酸化ナトリウム水溶
液でPH８に調整したのち、酢酸エチルで抽出し
た。この抽出液を飽和食塩水で洗浄後、無水硫酸
マグネシウムで乾燥し、酢酸エチルを留去する
と、Ｏ−（２，４−ジニトロフエニル）ヒドロキ
シルアミンが2.4ｇ得られた（収率81％）。
実施例 ７
Ｏ−（４−ニトロフエニル）アセトヒドロキサ
ム酸エチルエステル3.4ｇ（15ミリモル）をジオ
キサン30mlに溶かしたのち、50℃で75％硫酸水溶
液7.0ｇ（硫酸54ミリモル、水97ミリモル）を滴
下した。20℃で８時間撹拌後、反応混合物を水
100mlの中に投入した。次に５％水酸化ナトリウ
ム水溶液でPH10に調整したのち、酢酸エチルで抽
出した。その抽出液を飽和食塩水で洗浄後、無水
硫酸マグネシウムで乾燥し酢酸エチルを留去する
と、Ｏ−（４−ニトロフエニル）ヒドロキシルア
ミンが2.1ｇ得られた（収率91％）。
実施例 ８〜11
実施例７においてＯ−（４−ニトロフエニル）
アセトヒドロキサム酸エチルエステルの代りに表
２に示す
を用いる以外は実施例７と同様に反応を行つた。
結果を表１に示す。[Table] Example 6 O-(2,4-dinitrophenyl)acetohydroxamic acid ethyl ester 4.0 g (15 mmol)
After dissolving in 50 ml of dioxane, 13.5 g of cation exchange resin (trade name Amberlyst 15) and 1.7 g of water were added.
was added and stirred at 80°C for 6 hours. After cooling to room temperature, filter the cation exchange resin and add the liquid to 100ml of water.
I put it in. Next, the pH was adjusted to 8 with a 5% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. This extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off to obtain 2.4 g of O-(2,4-dinitrophenyl)hydroxylamine (yield: 81%). Example 7 After dissolving 3.4 g (15 mmol) of O-(4-nitrophenyl)acetohydroxamic acid ethyl ester in 30 ml of dioxane, 7.0 g of a 75% aqueous sulfuric acid solution (54 mmol of sulfuric acid, 97 mmol of water) was added dropwise at 50°C. . After stirring at 20°C for 8 hours, the reaction mixture was diluted with water.
Pour it into 100ml. Next, the pH was adjusted to 10 with a 5% aqueous sodium hydroxide solution, and then extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off to obtain 2.1 g of O-(4-nitrophenyl)hydroxylamine (yield 91%). Examples 8-11 O-(4-nitrophenyl) in Example 7
As shown in Table 2 instead of acetohydroxamic acid ethyl ester The reaction was carried out in the same manner as in Example 7 except that .
The results are shown in Table 1.
【表】
実施例 12
Ｏ−ピクリルアセトヒドロキサム酸エチルエス
テル4.7ｇ（15ミリモル）をジオキサン30mlに溶
かし、20℃で75％硫酸水溶液7.0ｇ（硫酸54ミリ
モル、水97ミリモル）を滴下した。20℃で７時間
撹拌後、反応混合物を氷水100mlの中に投入し、
析出物を取、乾燥すると、Ｏ−ピクリルヒドロ
キシルアミンが3.3ｇ得られた（収率90％）。[Table] Example 12 4.7 g (15 mmol) of O-picrylacetohydroxamic acid ethyl ester was dissolved in 30 ml of dioxane, and 7.0 g of a 75% aqueous sulfuric acid solution (54 mmol of sulfuric acid, 97 mmol of water) was added dropwise at 20°C. After stirring at 20°C for 7 hours, the reaction mixture was poured into 100ml of ice water.
The precipitate was collected and dried to obtain 3.3 g of O-picrylhydroxylamine (yield 90%).
Claims (1)
又はハロゲンで置換された低級アルキル基を、
R1およびR2は低級アルキル基を、ｎは１ないし
３の整数を示す。以下同様。）で表わされる化合
物をスルホン酸基含有化合物、スルホン酸基含有
陽イオン交換樹脂、フツ化水素酸および硝酸から
なる群より選ばれる物質の存在下に加水分解する
ことを特徴とする一般式（）、 で表わされるニトロフエノキシアミン類の製造方
法。[Claims] 1 General formula (), (In the formula, X is hydrogen, halogen, lower alkyl group, or lower alkyl group substituted with halogen,
R 1 and R 2 represent lower alkyl groups, and n represents an integer of 1 to 3. Same below. ) is hydrolyzed in the presence of a substance selected from the group consisting of a sulfonic acid group-containing compound, a sulfonic acid group-containing cation exchange resin, hydrofluoric acid, and nitric acid. , A method for producing nitrophenoxyamines represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59024992A JPS60169446A (en) | 1984-02-15 | 1984-02-15 | Production of nitrophenoxyamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59024992A JPS60169446A (en) | 1984-02-15 | 1984-02-15 | Production of nitrophenoxyamine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60169446A JPS60169446A (en) | 1985-09-02 |
| JPH043381B2 true JPH043381B2 (en) | 1992-01-23 |
Family
ID=12153470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59024992A Granted JPS60169446A (en) | 1984-02-15 | 1984-02-15 | Production of nitrophenoxyamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60169446A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4965390A (en) * | 1990-02-02 | 1990-10-23 | Ciba-Geigy Corporation | Hydroxamic acid esters |
| HK1077828A1 (en) * | 2002-07-11 | 2006-02-24 | Scios Inc. | Improved reagents for n-amination |
| GB0719180D0 (en) | 2007-10-02 | 2007-11-14 | Cambrex Karlskoga Ab | New process |
| WO2010116140A1 (en) * | 2009-04-08 | 2010-10-14 | Cambrex Karlskoga Ab | New process for preparing hydroxylamines and medicaments |
| CN111151303A (en) * | 2020-01-07 | 2020-05-15 | 东北师范大学 | Application of novel MIL-53(Fe) -based catalyst in removal of antibiotics in water |
-
1984
- 1984-02-15 JP JP59024992A patent/JPS60169446A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60169446A (en) | 1985-09-02 |
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