JP4479863B2 - N-monobromoisocyanuric acid metal salt hydrate and process for producing the same - Google Patents
N-monobromoisocyanuric acid metal salt hydrate and process for producing the same Download PDFInfo
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- JP4479863B2 JP4479863B2 JP01921799A JP1921799A JP4479863B2 JP 4479863 B2 JP4479863 B2 JP 4479863B2 JP 01921799 A JP01921799 A JP 01921799A JP 1921799 A JP1921799 A JP 1921799A JP 4479863 B2 JP4479863 B2 JP 4479863B2
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- salt hydrate
- hydrate
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- 229910052751 metal Inorganic materials 0.000 title claims description 11
- 239000002184 metal Substances 0.000 title claims description 11
- 150000003839 salts Chemical class 0.000 title claims description 11
- MWSLLEWOGABAFW-UHFFFAOYSA-N 1-bromo-1,3,5-triazinane-2,4,6-trione Chemical compound BrN1C(=O)NC(=O)NC1=O MWSLLEWOGABAFW-UHFFFAOYSA-N 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 2
- WYJXFFFWDRMGRG-UHFFFAOYSA-M [Na+].BrN1C(=O)NC(=O)[N-]C1=O Chemical compound [Na+].BrN1C(=O)NC(=O)[N-]C1=O WYJXFFFWDRMGRG-UHFFFAOYSA-M 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000005893 bromination reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000645 desinfectant Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- VRLDVERQJMEPIF-UHFFFAOYSA-N dbdmh Chemical compound CC1(C)N(Br)C(=O)N(Br)C1=O VRLDVERQJMEPIF-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、式（１）
【０００２】
【化２】
（式中、Ｍはアルカリ金属、ｎは０．１〜３を表す。）
で表されるＮ−モノブロモイソシアヌル酸金属塩水和物及びその製造法に関する。Ｎ−モノブロモイソシアヌル酸金属塩水和物は、工業有機化学品を選択的に臭素化する試剤として有用である。また、工業用殺菌剤や消毒剤として有用である。
【０００４】
【従来の技術】
従来、イミド型ブロム化剤としては、Ｎ−ブロモコハク酸（ＮＢＳ）や、１，３−ジブロモ−５，５−ジメチルヒダントインが知られている。しかし、これらは、ラジカル反応型臭素化剤のため臭素化位置選択性が必ずしも好ましくない。
【０００５】
また、ポーランド特許１６３４４１号に記載のＮ−モノブロモイソシアヌル酸ナトリウムは、臭素化反応の選択性は、改善されるものの、無水物であることから、吸水性があり、実用的には、保存安定性に問題があった。
【０００６】
【発明が解決しようとする課題】
芳香環やヘテロ環の特定の位置を臭素化する際にはイオン反応型臭素化剤が必要であり、本発明者らは上記の課題を解決するために種々の臭素化剤について鋭意研究した結果、高い位置選択性で臭素化するイオン型臭素化剤を見出し、本発明を完成した。
【０００７】
本発明の目的は、芳香環やヘテロ環の臭素化を高い位置選択性で行うことができるイオン型臭素化剤の提供にある。
【０００８】
【課題を解決するための手段】
本発明者は、上記課題を解決するため、鋭意研究を行った結果本発明を完成するに至った。
即ち本発明は、式（１）
【０００９】
【化３】
（式中、Ｍはアルカリ金属、ｎは０．１〜３を表す。）
で表されるＮ−モノブロモイソシアヌル酸金属塩水和物に関する。
また、シアヌル酸のアルカリ性水溶液に臭素を１０〜５０℃で反応させた後、二酸化炭素で中和し、析出した沈殿を濾取し、水洗後、２０〜６０℃で乾燥することを特徴とする前記式（１）で表されるＮ−モノブロモイソシアヌル酸金属塩水和物（以下ＳＭＢＩと略記する。）の製造法に関する。
以下、本発明を詳細に説明する。
【００１１】
【発明の実施の形態】
上記した本発明の化合物及びその製造法は次の反応式によって示される。
【００１２】
【化４】
（式中、Ｍはアルカリ金属、ｎは０．１〜３を表す。）
即ち、シアヌル酸（以下ＣＡと略記する。）をアルカリ金属水酸化物の水溶液に溶かし、シアヌル酸トリアルカリ金属塩（以下［中１］と略記する。）を得る。アルカリ金属塩の種類としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム及び水酸化セシウムが挙げられる。好ましくは、水酸化ナトリウム及び水酸化カリウムである。
アルカリ金属の使用量は、ＣＡに対して３．０〜３．３当量、より好ましくは３．０〜３．１当量である。
【００１４】
次に、得られた［中１］の水溶液中に臭素を滴下し、Ｎ−ブロモイソシアヌル酸二アルカリ金属塩（以下［中２］と略記する。）を得る。臭素の量は、ＣＡに対して１．０〜１．１当量、より好ましくは１．０〜１．０５当量である。臭素の添加速度は、滴下した臭素が脱色するのを確認して行うのが好ましい。反応時間は、滴下した臭素の色がほぼ消えた時間で反応終了とする。
【００１５】
更に［中２］に二酸化炭素を挿入し中和して、目的のＳＭＢＩが得られる。二酸化炭素の量は、ＣＡに対して１〜１．５当量、好ましくは１．１〜１．２当量である。反応温度は、５〜４０℃、好ましくは１０〜３０℃である。
【００１６】
次に、このスラリー液を濾過した後、結晶を水洗及び減圧乾燥する。温度は、２０〜６０℃、より好ましくは４０〜６０℃間で恒量になるまで行う。この温度で乾燥することにより付着水は除去され、ＳＭＢＩの３／２水和物で一定になる。この水和物は、室温解放系で静置させても吸湿することなく安定であった。この水分量は、Ｎ2気流中１２０℃でのカールフィッシャー法による測定と、ＴＧ熱分析での測定値から確認された。
【００１７】
ＳＭＢＩ製品が、付着水を含んで良い場合は、２０〜６０℃での乾燥を完全にせず、水分含量を３／２水和物以上することもできる。例えば付着水と結晶水を合わせてＳＭＢＩ・３水和物とすることができる。また、６０℃を越えた高い温度で減圧乾燥した場合は、結晶水含量をが３／２水和物以下から無水物まで減少させることもできる。例えばＳＭＢＩ・０．１水和物にすることもできる。但し、この場合は、大気下で吸湿性となり３／２水和物に戻って安定となる。
【００１８】
従って、実用的には、付着水を除いて、結晶水のみとしたＳＭＢＩ・３／２水和物まで乾燥することが製品管理上好ましい。
生成物のＳＭＢＩ・水和物の有効臭素量は、ヨウ素滴定法によって容易に測定することができる。
尚、本製造法は、連続法で実施することもできる。
【００１９】
【実施例】
以下に実施例を挙げ、本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
実施例１
水１５５ｍＬに水酸化ナトリウム１２ｇ（０．３モル）を溶解後、２５℃でシアヌル酸（ＣＡ）１２．９ｇ（０．１モル）を撹拌下に添加溶解させた。続いて、反応器を２０℃に冷却し、臭素８．０ｇ（０．１モル）を３０分かけて滴下した。その後、更に２５℃で３時間撹拌を継続し、臭素の色が完全に退色するのを確認した。次に、反応器を再び２０℃にやや冷却してから二酸化炭素ガス２．４６Ｌ（０．１１モル）を３０分間で送入した。二酸化炭素ガスの送入終了後、２５℃で１時間撹拌してから析出した白色結晶を濾過した。このケーキを水３０ｍＬで３回洗浄した後、４５℃で１０時間減圧乾燥し、白色結晶２５．６ｇを得た。この白色結晶の分析を以下の通り行った。
【００２０】
ＳＭＢＩ純度：ヨウ素滴定法：電位差自動滴定装置（京都電子工業社製）
（電極：＃１００−Ｍ１１１白金電極、＃１００−Ｒ１１６複合ガラス電極、
滴定液：１／１０Ｎａ2Ｓ2Ｏ4水溶液）
純度９１．０％
水分：カールフィシャー、１２０℃昇温法（乾燥空気気流下）（京都電子工業社製 ＭＫＣ−２１０）
９．０％（３／２水和物）
ＴＧ−ＤＴＡ：１５０．２〜１７４℃間に９．３重量％の重量減少が見られた。
【００２１】
従って、Ｎ−ブロモイソシアヌル酸ナトリウム３／２水和物が収率９９．５％で得られた。
このものは、６０℃で６時間再度減圧乾燥した。しかし重量減少は認められなかった。
【００２２】
参考例１
実施例１で得られたＮ−ブロモイソシアヌル酸ナトリウム・３／２水和物１０．０ｇを１２０℃の油浴で６時間減圧乾燥すると結晶重量は９．１０ｇで恒量になった。この乾燥品９．１０ｇをシャーレに採り、２５℃で２０時間、開放下で静置した結果、重量が１０．０ｇとなった。さらに２日間静置しても変わらなかった。
【００２３】
参考例２
実施例１で得られたＮ−ブロモイソシアヌル酸ナトリウム・３／２水和物１０．０ｇを参考例１と同様にシャーレに採り、２５℃で２０時間、開放下で静置した。しかし重量の変化は認められなかった。即ち、Ｎ−ブロモイソシアヌル酸ナトリウム無水物は、大気下に於いて容易に吸水するが、３／２水塩は、解放放置しても安定であった。
【００２４】
【発明の効果】
本発明のＮ−モノブロモイソシアヌル酸金属塩水和物は、保存安定性に優れた化合物であり、高い位置選択性で臭素化するイオン型臭素化剤である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to formula (1)
[0002]
[Chemical formula 2]
(In the formula, M represents an alkali metal, and n represents 0.1 to 3.)
N-monobromoisocyanuric acid metal salt hydrate represented by formula (1) and a process for producing the same. N-monobromoisocyanuric acid metal salt hydrate is useful as a reagent for selective bromination of industrial organic chemicals. Moreover, it is useful as an industrial disinfectant or disinfectant.
[0004]
[Prior art]
Conventionally, N-bromosuccinic acid (NBS) and 1,3-dibromo-5,5-dimethylhydantoin are known as imide-type brominating agents. However, since these are radical reaction brominating agents, the bromination regioselectivity is not always preferable.
[0005]
Further, sodium N-monobromoisocyanurate described in Polish Patent No. 163441 is an anhydride, although the selectivity of the bromination reaction is improved. There was a problem with sex.
[0006]
[Problems to be solved by the invention]
An ion-reactive brominating agent is necessary when brominating a specific position of an aromatic ring or a heterocycle, and the present inventors have conducted extensive research on various brominating agents in order to solve the above-mentioned problems. The present inventors have found an ionic brominating agent that brominates with high regioselectivity and completed the present invention.
[0007]
An object of the present invention is to provide an ionic brominating agent that can perform bromination of aromatic rings and hetero rings with high regioselectivity.
[0008]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present inventor has conducted extensive research and has completed the present invention.
That is, the present invention relates to the formula (1)
[0009]
[Chemical 3]
(In the formula, M represents an alkali metal, and n represents 0.1 to 3.)
N-monobromoisocyanuric acid metal salt hydrate represented by
In addition, bromine is reacted with an alkaline aqueous solution of cyanuric acid at 10 to 50 ° C., then neutralized with carbon dioxide, the deposited precipitate is collected by filtration, washed with water, and dried at 20 to 60 ° C. The present invention relates to a method for producing an N-monobromoisocyanuric acid metal salt hydrate (hereinafter abbreviated as SMBI) represented by the formula (1).
Hereinafter, the present invention will be described in detail.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
The above-described compound of the present invention and the production method thereof are shown by the following reaction formula.
[0012]
[Formula 4]
(In the formula, M represents an alkali metal, and n represents 0.1 to 3.)
That is, cyanuric acid (hereinafter abbreviated as CA) is dissolved in an aqueous solution of an alkali metal hydroxide to obtain a cyanuric acid trialkali metal salt (hereinafter abbreviated as [Middle 1]). Examples of the alkali metal salt include lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. Sodium hydroxide and potassium hydroxide are preferable.
The usage-amount of an alkali metal is 3.0-3.3 equivalent with respect to CA, More preferably, it is 3.0-3.1 equivalent.
[0014]
Next, bromine is dropped into the obtained [medium 1] aqueous solution to obtain N-bromoisocyanuric acid dialkali metal salt (hereinafter abbreviated as [medium 2]). The amount of bromine is 1.0 to 1.1 equivalents, more preferably 1.0 to 1.05 equivalents with respect to CA. The addition rate of bromine is preferably determined after confirming that the dropped bromine is decolorized. The reaction time is the time when the dropped bromine color has almost disappeared.
[0015]
Further, carbon dioxide is inserted into [Middle 2] and neutralized to obtain the target SMBI. The amount of carbon dioxide is 1 to 1.5 equivalents, preferably 1.1 to 1.2 equivalents, relative to CA. The reaction temperature is 5 to 40 ° C, preferably 10 to 30 ° C.
[0016]
Next, after filtering the slurry, the crystals are washed with water and dried under reduced pressure. The temperature is 20 to 60 ° C., more preferably 40 to 60 ° C. until a constant weight is reached. By drying at this temperature, the adhering water is removed and becomes constant with SMBI 3/2 hydrate. This hydrate was stable without moisture absorption even when allowed to stand in a room temperature open system. This water content was confirmed from the measurement by the Karl Fischer method at 120 ° C. in an N 2 gas stream and the measured value by TG thermal analysis.
[0017]
When the SMBI product may contain adhering water, drying at 20 to 60 ° C. is not complete, and the water content can be increased to 3/2 hydrate or more. For example, the adhering water and the crystal water can be combined to form SMBI trihydrate. In addition, when dried under reduced pressure at a high temperature exceeding 60 ° C., the water content of crystallization can be reduced from 3/2 hydrate or less to anhydride. For example, SMBI · 0.1 hydrate may be used. However, in this case, it becomes hygroscopic under the atmosphere and returns to 3/2 hydrate and becomes stable.
[0018]
Therefore, practically, it is preferable in terms of product management to dry to SMBI 3/2 hydrate containing only crystal water except for adhering water.
The effective bromine content of the product SMBI hydrate can be easily measured by the iodometric titration method.
In addition, this manufacturing method can also be implemented by a continuous method.
[0019]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
Example 1
After dissolving 12 g (0.3 mol) of sodium hydroxide in 155 mL of water, 12.9 g (0.1 mol) of cyanuric acid (CA) was added and dissolved at 25 ° C. with stirring. Subsequently, the reactor was cooled to 20 ° C., and 8.0 g (0.1 mol) of bromine was added dropwise over 30 minutes. Thereafter, stirring was further continued at 25 ° C. for 3 hours, and it was confirmed that the color of bromine was completely faded. Next, the reactor was again cooled slightly to 20 ° C., and then 2.46 L (0.11 mol) of carbon dioxide gas was fed in over 30 minutes. After the carbon dioxide gas was fed, the white crystals precipitated were filtered after stirring at 25 ° C. for 1 hour. The cake was washed 3 times with 30 mL of water and then dried under reduced pressure at 45 ° C. for 10 hours to obtain 25.6 g of white crystals. The white crystals were analyzed as follows.
[0020]
SMBI purity: iodine titration method: potentiometric automatic titrator (manufactured by Kyoto Electronics Co., Ltd.)
(Electrode: # 100-M111 platinum electrode, # 100-R116 composite glass electrode,
Titration solution: 1/10 Na 2 S 2 O 4 aqueous solution)
91.0% purity
Moisture: Karl Fischer, 120 ° C. heating method (under dry air flow) (MKC-210, manufactured by Kyoto Electronics Industry Co., Ltd.)
9.0% (3/2 hydrate)
TG-DTA: A weight loss of 9.3% by weight was observed between 150.2 and 174 ° C.
[0021]
Therefore, sodium N-bromoisocyanurate 3/2 hydrate was obtained with a yield of 99.5%.
This was again dried under reduced pressure at 60 ° C. for 6 hours. However, no weight reduction was observed.
[0022]
Reference example 1
When 10.0 g of sodium N-bromoisocyanurate · 3/2 hydrate obtained in Example 1 was dried under reduced pressure in an oil bath at 120 ° C. for 6 hours, the crystal weight became 9.10 g and a constant weight. 9.10 g of this dried product was taken in a petri dish and allowed to stand at 25 ° C. for 20 hours under open conditions, resulting in a weight of 10.0 g. It did not change even after standing for 2 days.
[0023]
Reference example 2
10.0 g of sodium N-bromoisocyanurate · 3/2 hydrate obtained in Example 1 was placed in a petri dish in the same manner as in Reference Example 1, and allowed to stand at 25 ° C. for 20 hours in an open state. However, no change in weight was observed. That is, sodium N-bromoisocyanurate anhydride readily absorbs water in the atmosphere, but 3/2 hydrate was stable even when left open.
[0024]
【The invention's effect】
The N-monobromoisocyanuric acid metal salt hydrate of the present invention is a compound having excellent storage stability and an ionic brominating agent that brominates with high regioselectivity.
Claims (3)
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| JP01921799A JP4479863B2 (en) | 1999-01-28 | 1999-01-28 | N-monobromoisocyanuric acid metal salt hydrate and process for producing the same |
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| JP01921799A JP4479863B2 (en) | 1999-01-28 | 1999-01-28 | N-monobromoisocyanuric acid metal salt hydrate and process for producing the same |
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| JP4479863B2 true JP4479863B2 (en) | 2010-06-09 |
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