JPS5929584B2 - Production method of ditertiary butyl hyponitrite - Google Patents
Production method of ditertiary butyl hyponitriteInfo
- Publication number
- JPS5929584B2 JPS5929584B2 JP3081274A JP3081274A JPS5929584B2 JP S5929584 B2 JPS5929584 B2 JP S5929584B2 JP 3081274 A JP3081274 A JP 3081274A JP 3081274 A JP3081274 A JP 3081274A JP S5929584 B2 JPS5929584 B2 JP S5929584B2
- Authority
- JP
- Japan
- Prior art keywords
- parts
- production method
- ditertiary butyl
- tertiary
- butyl hyponitrite
- 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
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- -1 butyl hyponitrite Chemical compound 0.000 title claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 6
- WCVVIGQKJZLJDB-UHFFFAOYSA-N o-butylhydroxylamine Chemical group CCCCON WCVVIGQKJZLJDB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- NFMHSPWHNQRFNR-UHFFFAOYSA-N hyponitrous acid Chemical compound ON=NO NFMHSPWHNQRFNR-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- IVVFFMGGGZBVNA-UHFFFAOYSA-N 2-methyl-2-[(2-methylpropan-2-yl)oxysulfamoylamino]oxypropane Chemical compound CC(C)(C)ONS(=O)(=O)NOC(C)(C)C IVVFFMGGGZBVNA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical group CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229910017974 NH40H Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- VDQQXEISLMTGAB-UHFFFAOYSA-N chloramine T Chemical compound [Na+].CC1=CC=C(S(=O)(=O)[N-]Cl)C=C1 VDQQXEISLMTGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- NSHIYIMHYBAIEY-UHFFFAOYSA-N ethyl hypochlorite Chemical compound CCOCl NSHIYIMHYBAIEY-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- ORQYPOUSZINNCB-UHFFFAOYSA-N potassium;hypobromite Chemical compound [K+].Br[O-] ORQYPOUSZINNCB-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- HNNKDQSGUCSXBD-UHFFFAOYSA-N propan-2-yl hypobromite Chemical compound C(C)(C)OBr HNNKDQSGUCSXBD-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は、第三級ブトキシアミンを、ハロゲン系酸化剤
を用いて酸化し、次亜硝酸ジ第三級ブチル（以下ＤＢＨ
Ｎと略称）を製造する方法に関すΣＣＨ３−Ｃ−Ｏ−Ｎ
Ｈ２＋Ｂｒ２−一ー→ Ｃ〔第三級ブトキシアミン〕
本発明に用いる第三級ブトキシアミンは、先ず、アンモ
ニヤ水と次亜塩素酸塩から公知の方法でモノクロルアミ
ンを得、次いで、これに、ナトリウム第三級ブチラート
を反応させることにより得ら＜る。DETAILED DESCRIPTION OF THE INVENTION The present invention oxidizes tertiary-butoxyamine using a halogen-based oxidizing agent to produce ditertiary-butyl hyponitrite (hereinafter referred to as DBH).
ΣCH3-C-O-N
H2+Br2--→C [Tertiary butoxyamine] The tertiary butoxyamine used in the present invention is obtained by first obtaining monochloroamine from aqueous ammonia and hypochlorite by a known method, and then adding sodium to this monochloramine. Obtained by reacting tertiary butyrate.
ＤＢＨＮは開始効率のすぐれた、適度の分解速度をもつ
、更に誘導分解を起さない興味ある重合開始剤として、
テトラヘドロンレターズ（１９６６年）６１６３頁等に
記載されてはいるが、従来次亜硝酸銀と臭化第三級ブチ
ルとの反応を経由する方法しか知られていず、特にその
次亜硝酸銀が合成困難で極めて高価、従つて実用化に到
らず、工業的に有用な製法が求められていた。DBHN is an interesting polymerization initiator with excellent initiation efficiency, moderate decomposition rate, and no induced decomposition.
Although it is described in Tetrahedron Letters (1966) p. 6163, the only known method is the reaction between silver hyponitrite and tertiary butyl bromide, and silver hyponitrite is particularly difficult to synthesize. However, it is extremely expensive and has therefore not been put into practical use, and an industrially useful manufacturing method has been sought.
本発明者らは、このような従来の製法の問題点を解消し
た、収率の良い、工業的に容易にＤＢＨＮを製造する新
規な製法を開発し、本発明を完成した。The present inventors have developed a new manufacturing method for producing DBHN industrially and easily with good yield, which solves the problems of such conventional manufacturing methods, and have completed the present invention.
即ち、本発明は、第三級ブトキシアミンと、ハロゲン系
酸化剤とを反応させることを特徴とする、次亜硝酸ジ第
三級ブチル（ＤＢＨＮ）の製法である。That is, the present invention is a method for producing ditertiary butyl hyponitrite (DBHN), which is characterized by reacting tertiary butoxyamine and a halogen-based oxidizing agent.
本発明に於て、例えば、ハロゲン系酸化剤として、臭素
を用いた場合の反応式は次のとおりである。In the present invention, for example, the reaction formula when bromine is used as the halogen-based oxidizing agent is as follows.
ＣＨ、ＣＨ３
Ｃ−０−Ｎ＝Ｎ−０−Ｃ−ＣＨ３＋ ２ＨＢにＣＨ、Ｃ
Ｈ３
〔ＤＢＨＮ〕
れる。CH, CH3 C-0-N=N-0-C-CH3+ CH, C in 2HB
H3 [DBHN].
ＮＨ４０Ｈ■ｆ−ＮａＣｌ０→ＣｌＮＨ２＋ＮａＯＨ＋
Ｈ２Ｏ・・ロゲン系酸化剤とは、塩素や臭素などの・・
ロゲン、次亜塩素酸ナトリウムや次亜臭素酸カリなどの
次亜ハロゲン酸塩、クロラミンＴ、次亜塩素酸エチルや
次亜臭素酸イソプロピルなどの次亜ハロゲン酸アルキル
など、通常の酸化剤が支障なく使用される。NH40H■f-NaCl0→ClNH2+NaOH+
H2O...Rogen-based oxidizing agents are chlorine, bromine, etc...
Common oxidizing agents such as chlorogens, hypohalites such as sodium hypochlorite and potassium hypobromite, chloramine T, and alkyl hypohalites such as ethyl hypochlorite and isopropyl hypobromite are problematic. used without.
反応に当つては、水、アルコール、炭化水素類など、通
常の溶媒系中で行うのが便利であり、使用酸化剤が安定
に作用する為にアルカリ性で行われるよう、僅量の無機
および有機のアルカリを添加するのが望ましく、温度は
−２０〜＋３０℃、更に好ましくは−１０〜＋１５℃を
選ぶが良く、このような条件では、反応完結までの所要
時間は１〜２時間で十分である。以下に実施例及び参考
例を示す。It is convenient to carry out the reaction in a normal solvent system such as water, alcohol, or hydrocarbons, and a small amount of inorganic and organic It is preferable to add an alkali of about 100 to 100°C, and the temperature is preferably -20 to +30°C, more preferably -10 to +15°C. Under these conditions, 1 to 2 hours is sufficient for the reaction to be completed. be. Examples and reference examples are shown below.
例中数量を示す部は重量部である。実施例
第三級ブトキシアミン２３部、水３００部、ピリジン７
８部の混液を攪拌、−５〜０℃で臭素７０部を滴下、更
に同温度で１．５時間反応して、反応物を氷水に注入、
瀘取、乾燥して、Ｍ．ｐ．８Ｏ〜８１℃（分解）のＤＢ
ＨＮｌ６部を収得。In the examples, the parts shown are parts by weight. Example 23 parts of tertiary butoxyamine, 300 parts of water, 7 parts of pyridine
8 parts of the mixed solution was stirred, 70 parts of bromine was added dropwise at -5 to 0°C, the mixture was further reacted at the same temperature for 1.5 hours, and the reactant was poured into ice water.
After filtering and drying, M. p. DB of 8O~81℃ (decomposition)
Obtained 6 parts of HNl.
参考例第三級ブトキシアミン２０部と正へキサン３６部
の混液を攪拌、Ｏ〜５℃で塩化スルフリル７．５部を滴
下して更に１時間反応、析出物を濾取乾燥して得たＭ．
ｐ．９９〜１０４℃のジ第三級ブトキシスルフアミド２
０部を、１２％次亜塩素酸ナトリウム水溶液１０４部、
水酸化ナトリウム７．８部、正ヘキサン１３部の混液へ
、０℃で撹拌下に滴下し、更に同温度で１時間反応、瀘
取水洗乾燥して１５部のＤＢＨＮを収得。Reference Example A mixed solution of 20 parts of tertiary butoxyamine and 36 parts of normal hexane was stirred, 7.5 parts of sulfuryl chloride was added dropwise at 0 to 5°C, the mixture was reacted for another hour, and the precipitate was filtered and dried. M.
p. Di-tert-butoxysulfamide 2 at 99-104°C
0 part, 104 parts of 12% sodium hypochlorite aqueous solution,
The mixture was added dropwise to a mixed solution of 7.8 parts of sodium hydroxide and 13 parts of hexane with stirring at 0°C, and the mixture was further reacted at the same temperature for 1 hour, filtered, washed with water, and dried to obtain 15 parts of DBHN.
Claims (1)
応させることを特徴とする、次亜硝酸ジ第三級ブチルの
製法。1. A method for producing ditertiary butyl hyponitrite, which is characterized by reacting tertiary butoxyamine and a halogen-based oxidizing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3081274A JPS5929584B2 (en) | 1974-03-18 | 1974-03-18 | Production method of ditertiary butyl hyponitrite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3081274A JPS5929584B2 (en) | 1974-03-18 | 1974-03-18 | Production method of ditertiary butyl hyponitrite |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5045984A Division JPS59186951A (en) | 1984-03-16 | 1984-03-16 | Production of di-tert-butyl hyponitrite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS50123624A JPS50123624A (en) | 1975-09-29 |
| JPS5929584B2 true JPS5929584B2 (en) | 1984-07-21 |
Family
ID=12314089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3081274A Expired JPS5929584B2 (en) | 1974-03-18 | 1974-03-18 | Production method of ditertiary butyl hyponitrite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929584B2 (en) |
-
1974
- 1974-03-18 JP JP3081274A patent/JPS5929584B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS50123624A (en) | 1975-09-29 |
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