KR20020008330A - Novel process for the preparation of 2-Bromo-2-nitro-1,3-propanediol - Google Patents
Novel process for the preparation of 2-Bromo-2-nitro-1,3-propanediol Download PDFInfo
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- C07C201/06—Preparation of nitro compounds
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- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
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- 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
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- C07C205/26—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by hydroxy groups and being further substituted by halogen atoms
Abstract
Description
미국특허 제 3,658,921호에서는 본 발명에서 사용되는 가성소다(Ⅲ) 대신 CaCl2·2H2O(V)를 사용하고 있는데 이를 사용하면 반응성이 낮아지고 부산물 처리가 어려운 단점이 있다.In US Pat. No. 3,658,921, CaCl 2 · 2H 2 O (V) is used instead of caustic soda (III) used in the present invention, which has a disadvantage of low reactivity and difficulty in treating by-products.
미국특허 제 3,771,561호에서는 가성소다(NaOH)를 분할 주입하는 공정이 공개되어 있는데 본 발명에 비하여 공정이 복잡해지는 단점이 있다.U.S. Patent No. 3,771,561 discloses a process of splitting caustic soda (NaOH), but the process is complicated compared to the present invention.
미국특허 제 3,771,561호에서는 브롬적하시 용매로서 사염화탄소나 이염화에틸렌을 적하한 후 아래층을 따라내고 용매층을 증류하여 목적 화합물을 제조하는 방법이 공개되어 있다. 이는 본 발명에 비하여 화학용매가 추가되며 용매를 증류하더라도 이 용매의 냄새가 목적물에 잔류할 소지가 있어 의약품 등의 용도로 사용할 경우 적합하지 않게된다.U.S. Patent No. 3,771,561 discloses a method of preparing a target compound by dropping carbon tetrachloride or ethylene dichloride as a solvent upon bromination, followed by pouring the lower layer and distilling the solvent layer. Compared to the present invention, the chemical solvent is added, and even if the solvent is distilled, the smell of the solvent may remain in the target product, and thus it is not suitable for use in medicine and the like.
미국특허 제 4,851,588호에서는 나이트로메탄(Ⅳ)에 3몰배의 포르말린(Ⅱ)을 사용하여 중간물질 트리스(하이드록시메틸)나이트로메탄을 제조하고, 이를 강산존재하에 케톤과 반응시킨후 염기화, 가수분해, 브롬화, 산처리등 다단계를 거치는공정이 공개되어 있다. 그러나 이러한 공정은 본 발명에 비해 복잡한 것이 큰 단점이다.US Pat. No. 4,851,588 prepares an intermediate tris (hydroxymethyl) nitromethane using 3 molar times formalin (II) in nitromethane (IV), and reacts it with ketone in the presence of a strong acid, followed by basicization, Processes that undergo multiple stages, such as hydrolysis, bromination, and acid treatment, have been disclosed. However, this process is a big disadvantage is that the complexity compared to the present invention.
또한 미국특허 제 4,922,030호에서는 나이트로메탄(Ⅳ)에 물 용매와 염기성 촉매하에서 브롬을 적하하고, 이를 정제하여 중간물질인 모노브로모니트로메탄을 얻고 이를 포르말린(Ⅱ)과 반응시켜 목적물질을 얻는 제조방법이 공개되어 있다 그러나 이방법에 의한 본 발명의 목적물질의 2단계 최종 수율은 66.5%에 불과하다.In addition, in US Pat. No. 4,922,030, bromine is added dropwise to nitromethane (IV) under a water solvent and a basic catalyst, and purified to obtain monobromonitromethane as an intermediate, which is then reacted with formalin (II) to obtain a target substance. The production method is disclosed, but the final yield of the second step of the target substance of the present invention by this method is only 66.5%.
본 발명은 하기 구조식(Ⅰ)로 표시되는 2-브로모-2-나이트로-1,3-프로판디올의 상업적 제조방법에 관한 것으로 기존의 제조방법에 비하여 공정을 단순화하고 사용 부원료를 최소화하는 방법에 관한 것이다.The present invention relates to a commercial preparation method of 2-bromo-2-nitro-1,3-propanediol represented by the following structural formula (I), which simplifies the process and minimizes the use of raw materials compared to the conventional production method. It is about.
본 발명의 첫번째 제조단계는 포르말린(Ⅱ)과 가성소다(Ⅲ)의 혼합에 이은 나이트로메탄(Ⅳ)의 적하로서 중간물질인 2-나이트로-1,3-프로판디올의 나트륨 염의 생성이다.The first production step of the present invention is the addition of formalin (II) and caustic soda (III) followed by the dropping of nitromethane (IV) to produce the sodium salt of the intermediate 2-nitro-1,3-propanediol.
본 발명의 두번째 제조공정은 브롬(Ⅶ)에 중간물질(Ⅷ)을 물 용매하에서 적하하는 공정으로, 일정온도와 시간이상에서는 서로 관계하여 부반응이 발생되며, 반대조건에서는 반응성이 낮아 지므로, 원료 투입량과 교반 효율성에 따라 정확한 반응시간과 온도 조절이 중요하며 또한 중간물질(Ⅷ)에 비해 과잉 주입되는 브롬의 비율도 중요하다.The second manufacturing process of the present invention is a process of dropping an intermediate in bromine in a water solvent, and side reactions occur in relation to each other at a predetermined temperature and time, and the reactivity is lowered under the opposite conditions, so that the amount of raw material input Accurate reaction time and temperature control are important, depending on the efficiency of the stirring and agitation, and the proportion of bromine overinjected relative to the intermediate is also important.
이하 본 발명을 더욱 상세히 설명하겠다.Hereinafter, the present invention will be described in more detail.
본 발명은 하기 구조식(Ⅰ)로 표시되는 2-브로모-2-나이트로-1,3-프로판디올의 제조방법에 있어서, 하기구조식(Ⅱ)로 표현되는 포르말린과 하기구조식(Ⅲ)로 표현되는 나이트로메탄의 혼합 용액에 하기 구조식(Ⅳ)로 표현되는 가성소다 수용액을 적하하여 하기 구조식(V)로 표현되는 2-나이트로-1,3-프로판디올 나트륨염의 수용액을 만들고 이것을 물을 용매로하여 하기 구조식(Ⅵ)로 표시되는 브롬에 0～12℃ 사이에서 서서히 적하하여 2-브로모-2-나이트로-1,3-프로판디올을 제조하는 것이다.The present invention is a method for producing 2-bromo-2-nitro-1,3-propanediol represented by the following structural formula (I), which is represented by formalin represented by the following structural formula (II) and the following structural formula (III) An aqueous solution of 2-nitro-1,3-propanediol sodium salt represented by the following structural formula (V) was added dropwise to an aqueous solution of caustic soda represented by the following structural formula (IV) to a mixed solution of nitromethane. The bromine represented by the following structural formula (VI) is gradually added dropwise between 0 to 12 ° C to prepare 2-bromo-2-nitro-1,3-propanediol.
HCHO ---------------------(Ⅱ)HCHO --------------------- (Ⅱ)
NaOH ---------------------(Ⅲ)NaOH --------------------- (Ⅲ)
CH3NO2---------------------(Ⅳ)CH 3 NO 2 --------------------- (Ⅳ)
CaCl2·2H2O ---------------------(Ⅴ)CaCl 2 · 2H 2 O --------------------- (Ⅴ)
Ca(OH)2---------------------(Ⅵ)Ca (OH) 2 --------------------- (Ⅵ)
Br2---------------------(Ⅶ)Br 2 --------------------- (Ⅶ)
여기서 상기 구조식(V)로 표시되는 2-나이트로-1,3-프로판디올의 나트륨염의 수용액을 제조하는데 있어서 상기 구조식(Ⅱ)로 표시되는 포르말린에 상기 구조식(Ⅲ)으로 표시되는 가성소다 용액을 혼합한 후, 상기 구조식(Ⅳ)로 표시되는 나이트로메탄을 25～35℃ 사이에서 적하한다.In preparing an aqueous solution of the sodium salt of 2-nitro-1,3-propanediol represented by the structural formula (V), the caustic soda solution represented by the structural formula (III) in formalin represented by the structural formula (II) After mixing, nitromethane represented by the above structural formula (IV) is added dropwise between 25 and 35 ° C.
또한 상기구조식(V)로 표시되는 2-나이트로-1,3-프로판디올의 나트륨염 수용액에 물을 용매로하여 상기 구조식(Ⅵ)으로 표시되는 브롬에 0～12℃로 적하하여 상기 구조식(Ⅰ)로 표시되는 2-브로모-2-나이트로-1,3-프로판디올을 제조한다. 기존의 브롬 회수방법은 하기 반응식(Ⅸ)과 같고 염소를 추가하여 NaBr염 중의 브롬을 회수하여 곧 바로 반응시키는 반응식은 반응식(Ⅹ)을 응용한 것으로 최종 반응식은 하기 반응식(XI)과 같다.In addition, water is used as a solvent in the sodium salt aqueous solution of 2-nitro-1,3-propanediol represented by the above structural formula (V), and dropwise to bromine represented by the above structural formula (VI) at 0 to 12 ° C. 2-Bromo-2-nitro-1,3-propanediol represented by I) was prepared. Conventional bromine recovery method is as shown in the following reaction formula (VII), the reaction of recovering the bromine in the NaBr salt immediately by adding chlorine is a reaction scheme (VII) is applied to the final reaction scheme is shown in the following reaction formula (XI).
그리고 위에서 제조된 상기 구조식(Ⅰ)로 표시되는 2-브로모-2-나이트로-1,3-프로판디올 수용액을 별도의 용매나 공정을 거치지 않고 -15 ～ -5℃ 사이에서 재결정하여 감압 여과하고 감압건조하여 최종 제품을 얻는다.And 2-bromo-2-nitro-1,3-propanediol aqueous solution represented by the above structural formula (I) is recrystallized between -15 ~ -5 ℃ without undergoing a separate solvent or a process under reduced pressure filtration Dry under reduced pressure to obtain the final product.
이하 실시예를 통하여 본 발명의 제조방법 및 그 효과에 대하여 구체적으로 설명하지다만 이것이 본 발명의 범주는 한정하는 것은 아니다.Hereinafter, the production method and effects of the present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited thereto.
[실시예 1]Example 1
3ℓ 플라스크에 포르말린 85g과 물 105g, 20% 가성소다 102g을 넣고 교반하면서 나이트로메탄 305g을 25～30℃ 사이에서 30분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 125g 추가하고 미리 준비된 브롬 410g에 0～5℃사이에서 1시간 30분 동안 적하하였다. 적하가 완료된 후 같은 온도에서 187g의 액화 염소를 45분간 주입하였다. 이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -10℃까지 냉각시킨후 감압하에 세척 여과한 후 건조시켜 목적물 845g을 얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 99.2%였다.Into a 3 L flask, 85 g of formalin, 105 g of water, and 102 g of 20% caustic soda were added and 305 g of nitromethane was added dropwise over 25 minutes while stirring. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 125 g of water was added to the white crystals to which the reaction was completed, and 410 g of bromine was previously added dropwise for 1 hour and 30 minutes at 0 to 5 ° C. After dropping was completed, 187 g of liquefied chlorine was injected at the same temperature for 45 minutes. This material is a pale red aqueous solution, neutralized with sodium hydrogen phosphate and turned into a white solution. The solution was cooled to −10 ° C., washed under reduced pressure, filtered, and dried to obtain 845 g of the desired product. This was analyzed by liquid chromatography and the purity was 99.2%.
[실시예 2]Example 2
3ℓ 플라스크에 포르말린 85g과 물 105g, 20% 가성소다 108g을 넣고 교반하면서 나이트로메탄 305g을 25～30℃ 사이에서 30분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 125g 추가하고 미리 준비된 브롬 410g에 0～5℃사이에서 1시간 30분 동안 적하하였다. 적하가 완료된 후 같은 온도에서 180g의 액화 염소를 50분간 주입하였다. 이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -10℃까지 냉각시킨후 감압여과한 후 건조시켜 목적물 845g을 얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 98.8%였다.Into a 3 L flask, 85 g of formalin, 105 g of water, and 108 g of 20% caustic soda were added and 305 g of nitromethane was added dropwise over 25 minutes while stirring. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 125 g of water was added to the white crystals to which the reaction was completed, and 410 g of bromine was previously added dropwise for 1 hour and 30 minutes at 0 to 5 ° C. After the dropping was completed, 180 g of liquid chlorine was injected for 50 minutes at the same temperature. This material is a pale red aqueous solution, neutralized with sodium hydrogen phosphate and turned into a white solution. The solution was cooled to −10 ° C., filtered under reduced pressure, and dried to obtain 845 g of the desired product. This was analyzed by liquid chromatography and the purity was 98.8%.
[실시예 3]Example 3
3ℓ 플라스크에 포르말린 85g과 물 105g, 20% 가성소다 102g을 넣고 교반하면서 나이트로메탄 312g을 25～30℃ 사이에서 30분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 125g 추가하고 미리 준비된 브롬 410g에 0～5℃사이에서 1시간 30분 동안 적하하였다. 이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -10℃까지 냉각시킨후 감압여과한 후 건조시켜 목적물 848g을 얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 99.3%였다.Into a 3 L flask, 85 g of formalin, 105 g of water, and 102 g of 20% caustic soda were added, and 312 g of nitromethane was added dropwise over 25 minutes while stirring. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 125 g of water was added to the white crystals to which the reaction was completed, and 410 g of bromine was previously added dropwise for 1 hour and 30 minutes at 0 to 5 ° C. This material is a pale red aqueous solution, neutralized with sodium hydrogen phosphate and turned into a white solution. The solution was cooled to −10 ° C., filtered under reduced pressure, and dried to obtain 848 g of the desired product. This was analyzed by liquid chromatography and the purity was 99.3%.
[실시예 4]Example 4
3ℓ 플라스크에 포르말린 85g과 물 105g, 20% 가성소다 102g을 넣고 교반하면서 나이트로메탄 305g을 25～30℃ 사이에서 30분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 125g 추가하고 미리 준비된 브롬 418g에 0～5℃사이에서 1시간 40분 동안 적하하였다. 이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -10℃까지 냉각시킨 후 감압여과한 후 건조시켜 목적물 844g을얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 98.7%였다.Into a 3 L flask, 85 g of formalin, 105 g of water, and 102 g of 20% caustic soda were added and 305 g of nitromethane was added dropwise over 25 minutes while stirring. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 125 g of water was added to the white crystals of which the reaction was completed, and 418 g of bromine, prepared in advance, was added dropwise for 1 hour and 40 minutes between 0 to 5 ° C. This material is a pale red aqueous solution, neutralized with sodium hydrogen phosphate and turned into a white solution. The solution was cooled to −10 ° C., filtered under reduced pressure, and dried to obtain 844 g of the desired product. This was analyzed by liquid chromatography and the purity was 98.7%.
[실시예 5]Example 5
3ℓ 플라스크에 포르말린 85g과 물 105g, 20% 가성소다 102g을 넣고 교반하면서 나이트로메탄 305g을 27～35℃ 사이에서 40분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 125g 추가하고 미리 준비된 브롬 413g에 0～5℃사이에서 1시간 30분 동안 적하하였다. 적하가 완료된 후 같은 온도에서 189g의 액화 염소를 40분간 주입하였다이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -10℃까지 냉각시킨 후 감압여과한 후 건조시켜 목적물 847g을 얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 99.0%였다.Into a 3 L flask, 85 g of formalin, 105 g of water, and 102 g of 20% caustic soda were added and 305 g of nitromethane was added dropwise over 27 minutes between 27 and 35 ° C. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 125 g of water was added to the white crystals to which the reaction was completed, and then dropwise to 413 g of bromine, prepared in advance, for 1 hour and 30 minutes. After the dropping was completed, 189 g of liquefied chlorine was injected at the same temperature for 40 minutes. This material was a light red aqueous solution, neutralized with sodium hydrogen phosphate, and changed to a white solution. The solution was cooled to −10 ° C., filtered under reduced pressure, and dried to obtain 847 g of the desired product. This was analyzed by liquid chromatography and the purity was 99.0%.
[실시예 6]Example 6
3ℓ 플라스크에 포르말린 85g과 물 105g, 20% 가성소다 102g을 넣고 교반하면서 나이트로메탄 305g을 30～35℃ 사이에서 30분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 125g 추가하고 미리 준비된 브롬 410g에 5～12℃사이에서 1시간 30분 동안 적하하였다. 이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -5℃까지 냉각시킨 후 감압여과한 후 건조시켜 목적물 842g을 얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 98.8%였다.Into a 3 L flask, 85 g of formalin, 105 g of water, and 102 g of 20% caustic soda were added and 305 g of nitromethane was added dropwise over 30 minutes while stirring. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 125 g of water was added to the white crystals to which the reaction was completed, and 410 g of bromine was previously added dropwise for 1 hour 30 minutes between 5 to 12 ° C. This material is a pale red aqueous solution, neutralized with sodium hydrogen phosphate and turned into a white solution. The solution was cooled to −5 ° C., filtered under reduced pressure and dried to obtain 842 g of the desired product. This was analyzed by liquid chromatography and the purity was 98.8%.
[실시예 7]Example 7
3ℓ 플라스크에 포르말린 85g과 물 110g, 20% 가성소다 102g을 넣고 교반하면서 나이트로메탄 305g을 25～30℃ 사이에서 30분에 걸쳐 적하하였다. 적하가 끝난 후 같은 온도에서 30분간 교반하면서 반응이 완료되기를 기다렸다. 반응이 완료된 흰색의 결정에 물을 120g 추가하고 미리 준비된 브롬 410g에 5～12℃사이에서 1시간 30분 동안 적하하였다. 이 물질은 연홍색의 수용액이며 인산수소나트륨으로 중화하여 백색 용액으로 변화시켰다. 이 용액을 -13℃까지 냉각시킨 후 감압여과한 후 건조시켜 목적물 849g을 얻었다. 이를 액체 크로마토그라피로 분석한 결과 순도는 98.9%였다.Into a 3 L flask, 85 g of formalin, 110 g of water, and 102 g of 20% caustic soda were added, and 305 g of nitromethane was added dropwise over 25 minutes while stirring. After the dropping was completed, the reaction was stirred at the same temperature for 30 minutes to complete the reaction. 120 g of water was added to the white crystals of which the reaction was completed, and 410 g of bromine prepared in advance was added dropwise for 1 hour 30 minutes between 5 to 12 ° C. This material is a pale red aqueous solution, neutralized with sodium hydrogen phosphate and turned into a white solution. The solution was cooled to −13 ° C., filtered under reduced pressure, and dried to obtain 849 g of the desired product. This was analyzed by liquid chromatography and the purity was 98.9%.
본 발명은 최적의 반응 온도와 최적의 반응 시간 및 원료물질을 선정하여 기존에 공개된 특허에 비하여 짧은 시간에 적은 종류의 원료와 공정으로 고순도, 고수율의 제품 제조가 가능하도록 한 것이다The present invention selects an optimal reaction temperature, an optimal reaction time, and raw materials to enable high purity and high yields of products with fewer types of raw materials and processes in a shorter time than previously disclosed patents.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711561A (en) * | 1969-10-28 | 1973-01-16 | Henkel & Cie Gmbh | Novel preparation of bromonitro alcohols |
| JPS4872108A (en) * | 1971-12-27 | 1973-09-29 | ||
| JPS56113745A (en) * | 1980-02-13 | 1981-09-07 | Kumiai Chem Ind Co Ltd | Preparation of bromonitroalcohol |
| JPS572242B2 (en) * | 1977-07-21 | 1982-01-14 | ||
| US5075510A (en) * | 1990-12-20 | 1991-12-24 | Great Lakes Chemical Corporation | Process for the preparation of bromonitro-alcohols |
| JPH061756A (en) * | 1992-06-18 | 1994-01-11 | K I Kasei Kk | Production of 1,3-propandiol derivative |
-
2000
- 2000-07-21 KR KR1020000042103A patent/KR20020008330A/en not_active Application Discontinuation
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3711561A (en) * | 1969-10-28 | 1973-01-16 | Henkel & Cie Gmbh | Novel preparation of bromonitro alcohols |
| JPS4872108A (en) * | 1971-12-27 | 1973-09-29 | ||
| JPS572242B2 (en) * | 1977-07-21 | 1982-01-14 | ||
| JPS56113745A (en) * | 1980-02-13 | 1981-09-07 | Kumiai Chem Ind Co Ltd | Preparation of bromonitroalcohol |
| US5075510A (en) * | 1990-12-20 | 1991-12-24 | Great Lakes Chemical Corporation | Process for the preparation of bromonitro-alcohols |
| JPH061756A (en) * | 1992-06-18 | 1994-01-11 | K I Kasei Kk | Production of 1,3-propandiol derivative |
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