JPH0780819B2 - Method for producing 2,2-dibromo-2-nitroethanol - Google Patents
Method for producing 2,2-dibromo-2-nitroethanolInfo
- Publication number
- JPH0780819B2 JPH0780819B2 JP3313831A JP31383191A JPH0780819B2 JP H0780819 B2 JPH0780819 B2 JP H0780819B2 JP 3313831 A JP3313831 A JP 3313831A JP 31383191 A JP31383191 A JP 31383191A JP H0780819 B2 JPH0780819 B2 JP H0780819B2
- Authority
- JP
- Japan
- Prior art keywords
- dibromo
- nitroethanol
- nitromethane
- solution
- mol
- 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 - Fee Related
Links
- FMNZAHDAULEOSO-UHFFFAOYSA-N 2,2-dibromo-2-nitroethanol Chemical compound OCC(Br)(Br)[N+]([O-])=O FMNZAHDAULEOSO-UHFFFAOYSA-N 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 239000000243 solution Substances 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003518 caustics Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000000034 method Methods 0.000 description 15
- OLQJQHSAWMFDJE-UHFFFAOYSA-N 2-(hydroxymethyl)-2-nitropropane-1,3-diol Chemical compound OCC(CO)(CO)[N+]([O-])=O OLQJQHSAWMFDJE-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 11
- 239000003513 alkali Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000031709 bromination Effects 0.000 description 5
- 238000005893 bromination reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LVDKZNITIUWNER-UHFFFAOYSA-N Bronopol Chemical compound OCC(Br)(CO)[N+]([O-])=O LVDKZNITIUWNER-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000006545 Ziziphus mauritiana Nutrition 0.000 description 2
- 240000000038 Ziziphus mauritiana Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QEVOQZYJNPFNRM-UHFFFAOYSA-N 1,1-dibromo-2-nitroethanol Chemical compound OC(Br)(Br)C[N+]([O-])=O QEVOQZYJNPFNRM-UHFFFAOYSA-N 0.000 description 1
- VUZPGEIXNYGDJN-UHFFFAOYSA-N 1-nitroethanol Chemical compound CC(O)[N+]([O-])=O VUZPGEIXNYGDJN-UHFFFAOYSA-N 0.000 description 1
- KIPMDPDAFINLIV-UHFFFAOYSA-N 2-nitroethanol Chemical compound OCC[N+]([O-])=O KIPMDPDAFINLIV-UHFFFAOYSA-N 0.000 description 1
- JENCTNRMNMTAHQ-UHFFFAOYSA-N Br.C[N+]([O-])=O Chemical compound Br.C[N+]([O-])=O JENCTNRMNMTAHQ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-AHCXROLUSA-N Bromine-79 Chemical compound [76Br] WKBOTKDWSSQWDR-AHCXROLUSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/16—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
- C07C205/13—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups
- C07C205/14—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms
- C07C205/15—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups having nitro groups and hydroxy groups bound to acyclic carbon atoms of a saturated carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、トリス（ヒドロキシメ
チル）ニトロメタンを出発原料として２，２−ジブロモ
−２−ニトロエタノールを高収率で製造する方法に関す
る。２，２−ジブロモ−２−ニトロエタノールは工業用
の殺菌剤や硫化物の除去剤として有効であり、これは、
例えば特開平２−２１３４３０２号、特開平２−１３５
１３８号等に記載されている。FIELD OF THE INVENTION The present invention relates to a method for producing 2,2-dibromo-2-nitroethanol in high yield using tris (hydroxymethyl) nitromethane as a starting material. 2,2-dibromo-2-nitroethanol is effective as an industrial germicide and sulfide remover, which is
For example, JP-A-2-2134302 and JP-A-2-135
No. 138, etc.
【０００２】[0002]
【従来の技術】２，２−ジブロモ−２−ニトロエタノー
ルの製造法としては、 ２−ブロモ−２−ニトロ−１，３−プロパンジオール
に次亜臭素酸カリウムを反応させる方法(Chemishe Beri
chte 57B, 2127〜2128(1924)) 。 ２−ブロモ−２−ニトロ−１，３−プロパンジオール
にアルコール溶液中アルコラートを反応させ、生成物を
取り出して乾燥エーテルに懸濁させて、これに臭素のク
ロロホルム溶液を加えて臭素化する方法(Chemishe Beri
chte 56B,611〜620(1923))。 ニトロメタン１モルに対し、１．５モル以上のホルム
アルデヒドを用い縮合させた後、臭素により臭素化する
方法（特開昭６１−２８９０６３号）。 ニトロメタンに臭素をアルカリの存在下で反応させた
後、ホルムアルデヒドを反応させる方法（特開平１−１
３２５４９号）。 等が知られている。2. Description of the Related Art As a method for producing 2,2-dibromo-2-nitroethanol, a method of reacting 2-bromo-2-nitro-1,3-propanediol with potassium hypobromite (Chemishe Beri
chte 57B, 2127-2128 (1924)). A method in which 2-bromo-2-nitro-1,3-propanediol is reacted with an alcoholate in an alcohol solution, the product is taken out and suspended in dry ether, and a chloroform solution of bromine is added thereto to brominate the product ( Chemishe Beri
chte 56B, 611-620 (1923)). A method in which 1.5 mol or more of formaldehyde is condensed with respect to 1 mol of nitromethane, and then bromination is performed with bromine (JP-A-61-289063). A method of reacting nitromethane with bromine in the presence of an alkali and then reacting with formaldehyde (JP-A-1-1)
32549). Etc. are known.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、これら
の従来の製造方法は次のような欠点を有し、工業的に実
施する方法としては必ずしも満足しうるものではない。
まず上記の２−ブロモ−２−ニトロ−１，３−プロパ
ンジオールに次亜臭素酸カリウムを反応させる方法は、
収率１０．７％（文献値）と著しく低く、全く工業的に
生産に適さない。However, these conventional manufacturing methods have the following drawbacks, and are not always satisfactory as industrial methods.
First, the method of reacting 2-bromo-2-nitro-1,3-propanediol with potassium hypobromite is
The yield is 10.7% (literature value), which is extremely low, and is not industrially suitable for production.
【０００４】の２−ブロモ−２−ニトロ−１，３−プ
ロパンジオールを出発原料とする方法は操作が煩雑であ
るばかりでなく収率２１％（文献値）と著しく低く、や
はり工業的生産に適さない。のニトロメタンにホルマ
リンを縮合させた後に臭素化する方法は、特開昭６１−
２８９０６３号の実施例１の追試を行ったところ、分液
油状物の２，２−ジブロモ−２−ニトロエタノール含有
率５７．３〜６２．２％で、かつ、ニトロメタン基準の
収率３６．６〜３７．２％であり、品質及び収率面で工
業的な生産に十分とはいえなかった。The method using 2-bromo-2-nitro-1,3-propanediol as a starting material is not only complicated in operation, but also has a yield of 21% (reference value), which is extremely low, and is also suitable for industrial production. Not suitable. The method of condensing formalin to nitromethane and then brominating is disclosed in JP-A-61-161
When an additional test of Example 1 of No. 289063 was performed, the separated oily substance had a 2,2-dibromo-2-nitroethanol content of 57.3 to 62.2% and a yield of 36.6 based on nitromethane. It was ~ 37.2%, which was not sufficient for industrial production in terms of quality and yield.
【０００５】さらにのニトロメタン臭素化物にホルマ
リンを縮合させる方法は、特開平１−１３２５４９号の
実施例１に基づいて追試を行ったところ、同公報の記載
にもかかわらず、２，２−ジブロモ−２−ニトロ−１−
エタノールがほとんど生成しなかった。A further method for condensing formalin to a nitromethane bromide was conducted as an additional test based on Example 1 of JP-A-1-132549. Despite the description in the publication, 2,2-dibromo- 2-nitro-1-
Almost no ethanol was produced.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の工
業化の問題点を解決すべく鋭意研究を重ねた結果、トリ
ス（ヒドロキシメチル）ニトロメタンを出発原料とし、
水溶媒中アルカリ分解後、臭素化し、その後ｐＨ調整を
行うことにより高収率で２，２−ジブロモ−２−ニトロ
エタノールが得られることを見い出し、この知見に基づ
き本発明をなすに至った。Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of industrialization, the present inventors have used tris (hydroxymethyl) nitromethane as a starting material,
It was found that 2,2-dibromo-2-nitroethanol can be obtained in high yield by alkaline decomposition in a water solvent, bromination, and then pH adjustment, and the present invention has been completed based on this finding.
【０００７】すなわち本発明は、水溶液中でトリス（ヒ
ドロキシメチル）ニトロメタンに苛性アルカリを反応さ
せ、次いでこの反応物に臭素を反応させた後、反応液の
ｐＨを７以下に調整することを特徴とする２，２−ジブ
ロモ−２−ニトロエタノールの製造法を提供するもので
ある。本発明方法における全反応は、次式に従うと考え
られる。That is, according to the present invention, tris (hydroxymethyl) nitromethane is reacted with caustic in an aqueous solution, and then this reaction product is reacted with bromine .
The present invention provides a method for producing 2,2-dibromo-2-nitroethanol, which is characterized by adjusting pH to 7 or less . All reactions in the process of the invention are believed to follow the formula:
【０００８】[0008]
【化１】 [Chemical 1]
【０００９】本発明において、まず、トリス（ヒドロキ
シメチル）ニトロメタンを水溶液として、苛性アルカリ
を反応させる。この第１段階の反応は、トリス（ヒドロ
キシメチル）ニトロメタンのアルカリによる造塩反応で
ある。アルカリとしては、水酸化ナトリウム、水酸化カ
リウム、水酸化リチウム、水酸化カルシウム、水酸化マ
グネシウム、水酸化バリウム等があげられるが、反応性
などの上から水酸化ナトリウムや水酸化カリウム等の苛
性アルカリが好ましい。アルカリ処理の反応温度は、−
１０〜６０℃、好ましくは０〜４０℃で、アルカリはト
リス（ヒドロキシメチル）ニトロメタンに対し、好まし
くは２．５倍モル以上、より好ましくは３．０〜３．３
倍モル用いる。In the present invention, first, tris (hydroxymethyl) nitromethane is used as an aqueous solution and reacted with caustic. This first step reaction is a salt formation reaction of tris (hydroxymethyl) nitromethane with an alkali. Examples of the alkali include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide and the like. Is preferred. The reaction temperature for alkali treatment is −
At 10 to 60 ° C., preferably at 0 to 40 ° C., the alkali is preferably 2.5 times mol or more, more preferably 3.0 to 3.3, based on tris (hydroxymethyl) nitromethane.
Use twice the molar amount.
【００１０】苛性アルカリは、生成する２，２−ジブロ
モ−２−ニトロエタノールがアルカリと塩を形成するた
めに必要であり、２．０モル当量ではアルカリが不足し
反応が十分進行しないことがある。反応溶媒としては、
水のみ、あるいは水・アルコール混合系を用いることが
できるが、副生する臭化金属塩の溶解度の関係から水単
独系が好ましい。また爆発等の危険があるので安全面か
らも水単独系が有利である。The caustic alkali is necessary for the 2,2-dibromo-2-nitroethanol produced to form a salt with the alkali. At 2.0 molar equivalents, the alkali may be insufficient and the reaction may not proceed sufficiently. . As the reaction solvent,
Water alone or a water / alcohol mixed system can be used, but a water alone system is preferable in view of the solubility of the metal bromide salt produced as a by-product. In addition, since there is a risk of explosion and the like, the water-only system is advantageous in terms of safety.
【００１１】次に、第２段の反応として臭素化を行う。
これは第１段の反応液から生成物を分離することなく、
そのまま、臭素を滴下して行うことができる。この臭素
化はトリス（ヒドロキシメチル）ニトロメタンに対し
て、理論量に近い２．０倍モル以上、好ましくは２．０
〜２．３倍モルの臭素化剤を用いる。臭素化後の反応液
を酸によりｐＨ調整してｐＨ７以下、好ましくはｐＨ３
以下として終了する。反応液をアルカリ性のまま終了す
ると、２，２−ジブロモ−２−ニトロエタノールのアル
カリ分解が起こり、収率低下の要因となることがある。
中和に用いる酸は、特に制限はないが塩酸や硫酸等の無
機酸が好ましい。Then, bromination is carried out as a second stage reaction.
Without separating the product from the first stage reaction,
As it is, bromine can be added dropwise. This bromination is 2.0 times mol or more, preferably 2.0 times or more, close to the theoretical amount with respect to tris (hydroxymethyl) nitromethane.
~ 2.3 times mole of brominating agent is used. The pH of the reaction solution after bromination is adjusted with an acid to pH 7 or less, preferably pH 3
The following ends. If the reaction solution is left alkaline, 2,2-dibromo-2-nitroethanol may be decomposed by alkali, which may cause a decrease in yield.
The acid used for neutralization is not particularly limited, but inorganic acids such as hydrochloric acid and sulfuric acid are preferable.
【００１２】かくして、得られる２，２−ジブロモ−２
−ニトロエタノール油状物及び水層をトルエン、クロロ
ホルム等の溶剤で抽出し、水洗精製すれば、容易に高収
率で高純度の２，２−ジブロモ−２−ニトロエタノール
を得ることができる。The 2,2-dibromo-2 thus obtained
By extracting the nitroethanol oil and the aqueous layer with a solvent such as toluene and chloroform and washing with water and purifying, 2,2-dibromo-2-nitroethanol of high purity can be easily obtained in high yield.
【００１３】[0013]
【発明の効果】本発明方法によれば、比較的コストの低
廉で、入手しやすい化合物であるトリス（ヒドロキシメ
チル）ニトロメタンを原料にして、２，２−ジブロモ−
２−ニトロエタノールを高収率で、かつ、高純度で得る
ことができる。さらに反応溶媒が水性であるので、工程
の安全性が高い。したがって本発明方法は工業的に実施
する方法として極めて好適である。According to the method of the present invention, 2,2-dibromo- is prepared by using tris (hydroxymethyl) nitromethane, which is a relatively inexpensive and easily available compound, as a raw material.
2-Nitroethanol can be obtained in high yield and high purity. Furthermore, since the reaction solvent is aqueous, the process safety is high. Therefore, the method of the present invention is extremely suitable as a method to be carried out industrially.
【００１４】[0014]
【実施例】次に、本発明を実施例に基づきさらに詳細に
説明する。 実施例１〜３ 温度計、冷却管、滴下ロート、撹拌機を備えた四つ口フ
ラスコに、５０％トリス（ヒドロキシメチル）ニトロメ
タン７５．５ｇ（０．２５モル）と水７５ｇを仕込み撹
拌しながら、１５℃以下になるまで冷却した。次いで滴
下ロートから４８％水酸化ナトリウム水溶液６８．８ｇ
（０．８３モル）を５〜１５℃に保ち、ゆっくり滴下す
る。EXAMPLES Next, the present invention will be described in more detail based on examples. Examples 1 to 3 A four-necked flask equipped with a thermometer, a cooling tube, a dropping funnel, and a stirrer was charged with 75.5 g (0.25 mol) of 50% tris (hydroxymethyl) nitromethane and 75 g of water while stirring. It was cooled to 15 ° C or lower. Then, from the dropping funnel, 68.8 g of 48% aqueous sodium hydroxide solution
(0.83 mol) is kept at 5 to 15 ° C., and the solution is slowly added dropwise.
【００１５】次に、滴下終了後の反応液へ臭素９１．９
ｇ（０．５８モル）を０〜５℃に保ちながらゆっくり滴
下した。滴下終了後３０分間撹拌熟成してから、３５％
塩酸を滴下し、反応液をｐＨ１へ調整した。反応液を分
液ロートへ移し静置すると、上層の水層及び下層の油状
物に分液するので、別々に採取し、水層はトルエン５０
ｇで２回抽出処理した。また油状物は、トルエン１５０
ｇに溶解後、水５０ｇで水洗処理する。水洗水は、さら
にトルエン２５ｇで抽出処理した。各トルエン層をまと
めてトルエンを減圧回収除去すると残留物として精製さ
れた２，２−ジブロモ−２−ニトロエタノールが得られ
た。この反応条件で、水酸化ナトリウムと臭素のモル比
を変えて反応させた結果を表１に示す。この表の結果よ
り精製品で収率約７４％以上を示していることが分る。
なお、油状物及び精製品の２，２−ジブロモ−２−ニト
ロエタノールの含有率は、内部標準法のガスクロマトグ
ラフ法により定量した。また、収率はトリス（ヒドロキ
シメチル）ニトロメタンを基準として求めた。Then, bromine 91.9 is added to the reaction solution after the dropping.
g (0.58 mol) was slowly added dropwise while maintaining 0 to 5 ° C. 35% after stirring and aging for 30 minutes after completion of dropping
Hydrochloric acid was added dropwise to adjust the reaction solution to pH 1. When the reaction solution is transferred to a separating funnel and allowed to stand still, it separates into an upper aqueous layer and a lower oily substance.
It was extracted twice with g. The oily substance is toluene 150
After being dissolved in 50 g, it is washed with 50 g of water. The washing water was extracted with 25 g of toluene. The toluene layers were collected and removed under reduced pressure to obtain 2,2-dibromo-2-nitroethanol purified as a residue. Table 1 shows the reaction results obtained by changing the molar ratio of sodium hydroxide and bromine under these reaction conditions. The result of this table
It can be seen that the purified product shows a yield of about 74% or more.
The content of 2,2-dibromo-2-nitroethanol in the oily substance and the purified product was quantified by the gas chromatography method as an internal standard method. The yield was calculated based on tris (hydroxymethyl) nitromethane.
【００１６】[0016]
【表１】 [Table 1]
【００１７】実施例４〜５ 水酸化ナトリウムの代りに等モルの水酸化カリウムを用
いた以外は実施例１と全く同様にして２，２−ジブロモ
−２−ニトロエタノールを製造した。その結果を表２に
示した。Examples 4 to 5, 2,2-dibromo-2-nitroethanol was produced in exactly the same manner as in Example 1 except that equimolar potassium hydroxide was used instead of sodium hydroxide. The results are shown in Table 2.
【００１８】[0018]
【表２】 [Table 2]
【００１９】実施例６ ４８％水酸化ナトリウム水溶液の滴下温度を２５〜３５
℃とした以外は実施例１と全く同様にして２，２−ジブ
ロモ−２−ニトロエタノールを製造した。その結果を表
３に示した。Example 6 The dropping temperature of a 48% aqueous sodium hydroxide solution was adjusted to 25 to 35.
2,2-Dibromo-2-nitroethanol was produced in exactly the same manner as in Example 1 except that the temperature was changed to ° C. The results are shown in Table 3.
【００２０】[0020]
【表３】 [Table 3]
【００２１】比較例１ 冷却管、滴下ロート、温度計及び撹拌機を備えた四つ口
フラスコにニトロメタン１５．３ｇ（０．２５モル）、
水３７．５ｇ及び３７％ホルムアルデヒド水溶液４０．
６ｇ（０．５モル）を加える。この混合液を撹拌しなが
ら冷却し、２５％水酸化ナトリウム水溶液８０．０ｇ
（０．５モル）を−５℃〜０℃に保ちながら滴下した。
滴下終了後、１時間熟成撹拌を続けてから、臭素７９．
９ｇ（０．５モル）を０〜５℃に保ちながら滴下した。
反応液を分液ロートに移して静置すると分液するので、
油状物及び水層を採取し、実施例１同様の後処理と分析
により収量及び収率を求めた結果を表４に示す。この方
法によれば精製品の場合で収率４７．９％と低い値を示
した。この反応は、合計３回繰り返したが同様の結果が
得られた。なお、収率はニトロメタン基準により算出し
たものである。Comparative Example 1 Cooling tube,Dripping funnel,Four mouths with thermometer and stirrer
15.3 g (0.25 mol) of nitromethane in the flask,
Water 37.5 g and 37% aqueous formaldehyde solution 40.
6g(0.5 mol) is added. While stirring this mixture
Cooled, 25% aqueous sodium hydroxide solution 80.0g
(0.5 mol) was added dropwise while maintaining at -5 ° C to 0 ° C.
After completion of dropping, the mixture was aged and stirred for 1 hour, and then bromine 79.
9 g (0.5 mol) was added dropwise while maintaining at 0 to 5 ° C.
When the reaction solution is transferred to a separating funnel and left standing, it separates.
The oily substance and the aqueous layer were collected and subjected to the same post-treatment and analysis as in Example 1.
The yield and the results obtained byFourShown in.This person
According to the method, the yield was 47.9%, which was low for purified products.
did.This reaction was repeated 3 times in total, but similar results were obtained.
Was obtained. The yield is calculated based on the nitromethane standard.
It is a thing.
【００２２】[0022]
【表４】 [Table 4]
【００２３】比較例２ 温度計、冷却器、滴下ロート、撹拌機を備えた四つ口フ
ラスコに５０％トリス（ヒドロキシメチル）ニトロメタ
ン７５．５ｇ（０．２５モル）と水７５ｇを仕込み、１
５℃以下になるまで冷却した。別に、４８％水酸化ナト
リウム水溶液６８．８ｇ（０．８３モル）へ冷却しなが
ら、臭素９１．９ｇ（０．５８モル）を滴下し、次亜臭
素酸ナトリウム溶液を調整する。この次亜臭素酸ナトリ
ウム溶液を滴下ロートに入れ、先に準備したトリス（ヒ
ドロキシメチル）ニトロメタンの水溶液中へ０〜５℃に
保ちながらゆっくり滴下した。滴下終了後、３０分間撹
拌熟成してから、３５％塩酸を滴下し、ｐＨ１へ調整す
る。反応液を分液ロートへ移し静置したが、油状物の分
液がなく、かつ、反応液中の２，２−ジブロモ−２−ニ
トロエタノールを分析したが検出されなかった。Comparative Example 2 A four-necked flask equipped with a thermometer, a condenser, a dropping funnel, and a stirrer was charged with 50% tris (hydroxymethyl) nitromethane (75.5 g, 0.25 mol) and water (75 g).
It cooled until it became 5 degrees C or less. Separately, while cooling to a 48% aqueous sodium hydroxide solution of 68.8 g (0.83 mol), 91.9 g (0.58 mol) of bromine is added dropwise to prepare a sodium hypobromite solution. This sodium hypobromite solution was placed in a dropping funnel and slowly added dropwise to the previously prepared aqueous solution of tris (hydroxymethyl) nitromethane while maintaining the temperature at 0 to 5 ° C. After completion of the dropping, the mixture is stirred and aged for 30 minutes, and then 35% hydrochloric acid is added dropwise to adjust the pH to 1. The reaction solution was transferred to a separating funnel and allowed to stand still, but there was no separation of an oily substance, and 2,2-dibromo-2-nitroethanol in the reaction solution was analyzed but was not detected.
【００２４】比較例３ 冷却管、滴下ロート、温度計及び撹拌機を備えた四つ口
フラスコに５０％トリス（ヒドロキシメチル）ニトロメ
タン７５．５ｇ（０．２５モル）と水７５ｇを仕込み、
撹拌しながら１５℃以下になるまで冷却した。２０％炭
酸ナトリウム水溶液４３９．９ｇ（０．８３モル）を５
〜１５℃に保ちながらゆっくり滴下した。次いで、滴下
終了後の反応液へ臭素９１．９ｇ（０．５８モル）を０
〜５℃に保ちながらゆっくり滴下した。滴下終了後、３
０分撹拌熟成してから、３５％塩酸を滴下し、反応液を
ｐＨ１へ調整した。反応液を分液ロートへ移して静置し
たが、油状物の分離がなく、かつ、反応液中の２，２−
ジブロモ−２−ニトロエタノールを分析した結果、検出
されなかった。Comparative Example 3 A four-necked flask equipped with a cooling tube, a dropping funnel, a thermometer and a stirrer was charged with 75.5 g (0.25 mol) of 50% tris (hydroxymethyl) nitromethane and 75 g of water.
It was cooled to 15 ° C or lower with stirring. 20% sodium carbonate aqueous solution 439.9 g (0.83 mol) was added to 5
The solution was slowly added dropwise while keeping at -15 ° C. Next, 91.9 g (0.58 mol) of bromine was added to the reaction solution after the dropping was completed.
The solution was slowly added dropwise while keeping at -5 ° C. After dropping, 3
After stirring and aging for 0 minutes, 35% hydrochloric acid was added dropwise to adjust the reaction solution to pH 1. The reaction solution was transferred to a separating funnel and allowed to stand still, but there was no separation of an oily substance, and 2,2-
As a result of analyzing dibromo-2-nitroethanol, it was not detected.
Claims (1)
ニトロメタンに苛性アルカリを反応させ、次いでこの反
応物に臭素を反応させた後、反応液のｐＨを７以下に調
整することを特徴とする２，２−ジブロモ−２−ニトロ
エタノールの製造法。1. Tris (hydroxymethyl) in an aqueous solution
After reacting nitromethane with caustic and then reacting this reaction product with bromine, the pH of the reaction solution was adjusted to 7 or less.
A method for producing 2,2-dibromo-2-nitroethanol, which comprises:
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/915,665 US5243092A (en) | 1991-09-11 | 1992-07-21 | Method for producing 2,2-dibromo-2-nitroethanol |
| KR1019920016220A KR960015808B1 (en) | 1991-09-11 | 1992-09-05 | Method for preparing 2,2-dibromo-2-nitroethanol |
| EP92115342A EP0531936B1 (en) | 1991-09-11 | 1992-09-08 | Method for producing 2,2-dibromo-2-nitroethanol |
| DE69210723T DE69210723T2 (en) | 1991-09-11 | 1992-09-08 | Process for the preparation of 2,2-dibromo-2-nitroethanol |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-258654 | 1991-09-11 | ||
| JP25865491 | 1991-09-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05125022A JPH05125022A (en) | 1993-05-21 |
| JPH0780819B2 true JPH0780819B2 (en) | 1995-08-30 |
Family
ID=17323258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3313831A Expired - Fee Related JPH0780819B2 (en) | 1991-09-11 | 1991-10-31 | Method for producing 2,2-dibromo-2-nitroethanol |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH0780819B2 (en) |
| KR (1) | KR960015808B1 (en) |
-
1991
- 1991-10-31 JP JP3313831A patent/JPH0780819B2/en not_active Expired - Fee Related
-
1992
- 1992-09-05 KR KR1019920016220A patent/KR960015808B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| KR930005964A (en) | 1993-04-20 |
| JPH05125022A (en) | 1993-05-21 |
| KR960015808B1 (en) | 1996-11-21 |
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