KR101703008B1 - - method for environmentally-friendly -bromination of phenyl alkyl ketone derevatives - Google Patents
- method for environmentally-friendly -bromination of phenyl alkyl ketone derevatives Download PDFInfo
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- KR101703008B1 KR101703008B1 KR1020150048231A KR20150048231A KR101703008B1 KR 101703008 B1 KR101703008 B1 KR 101703008B1 KR 1020150048231 A KR1020150048231 A KR 1020150048231A KR 20150048231 A KR20150048231 A KR 20150048231A KR 101703008 B1 KR101703008 B1 KR 101703008B1
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Abstract
본 발명은 1)브로민화 수소산 수용액에 염소산나트륨을 포함하는 산화제를 첨가 및 교반하여 브로민을 합성하는 단계; 및 2) 하기 화학식 1로 기재되는 페닐 알킬 케톤 유도체를 출발물질로 하여, 상기 1) 단계의 브로민화 반응을 이용해 페닐 알킬 α-브로모 케톤 유도체를 합성하는 단계; 를 포함하는 친환경적이고, 효율적인 페닐 알킬 케톤 유도체의 α-브로민화 방법에 관한 것이다. The present invention relates to a method for producing bromine, comprising: 1) synthesizing bromine by adding and stirring an oxidizing agent containing sodium chlorate to an aqueous solution of hydrobromic acid; And 2) synthesizing a phenylalkyl? -Bromo ketone derivative using the phenylalkyl ketone derivative represented by the following formula (1) as a starting material, using the bromination reaction in step 1); And a method for? -Bromination of an environmentally-friendly, efficient phenylalkylketone derivative.
Description
본 발명은 페닐 알킬 케톤 유도체를 출발물질로 하는 α-브로민화 반응에 관한 것 에 관한 것이다.
The present invention relates to an? -Bromination reaction using a phenylalkylketone derivative as a starting material.
다양한 유기반응에서 브로민 작용기를 갖는 물질들은 다음단계 반응을 위한 전구물질로 널리 사용되고 있다. 그러나 브로민을 직접 사용하는 브로민화 반응은 작업자의 안전을 보장하기 어렵고 취급에 상당한 주의가 요구되어 생산 공정에 적용하기를 기피하고 있어, 노동집약적 국가들의 강력한 도전을 받고 있는 분야이다.In a variety of organic reactions, materials with bromine functionality are widely used as precursors for the next step reaction. However, the bromination reaction, which uses bromine directly, is a challenging area for labor-intensive countries because it is difficult to ensure the safety of workers and requires careful handling and avoids application to production processes.
브로민화 반응과 관련하여 선행기술문헌 1은 산화제인 H2O2를 이용하고, 반응 진행 중 HBr을 산화시켜 생성된 브로민을 이용하여 브롬화가 진행되는 반응이다. 그러나 반응시간이 8~24시간 정도로 길게 소요된다. 또한 NH4Br 및 옥손(Oxone)을 사용하여 브로민화하는 반응이 알려져 있으나(선행기술문헌 2), 반응이 완결되는데 걸리는 시간이 길고, 수율이 낮은 문제가 있다. 또한 NBS, TsOH 및 CH3CN을 사용하는 반응이 있으나(선행기술문헌 3), 브로민화 반응 진행에 있어 고가의 N-bromosuccinimide를 사용하기 때문에 경제성이 떨어진다. 뿐만 아니라, K2S2O8 및 KBr을 이용한 브로민화 반응이 있으나(선행기술 4), 반응이 완결되는데 걸리는 시간이 12시간으로 길고, 반응 진행시 열을 가해주어야 하는 단점이 있다. 또한 종래 브로민화 반응에서 브로민(Br2)을 직접 사용하는 방법은(선행기술 5) 작업자의 안전을 보장하기 어렵고 취급에 상당한 주의가 요구되어 생산 공정에 적용하기를 기피하고 있다. 한편, N-bromosuccinimide (NBS)를 사용할 경우 원자재 값 상승의 주된 원인으로 경제성이 떨어진다. In relation to the bromination reaction, Prior Art Document 1 is a reaction in which bromine is generated using bromine generated by oxidizing HBr during the reaction using H 2 O 2 which is an oxidizing agent. However, the reaction time is as long as 8 ~ 24 hours. Also, the reaction of brominating with NH 4 Br and oxone is known (Prior Art Document 2), but the time required for completion of the reaction is long and the yield is low. In addition, although there is a reaction using NBS, TsOH and CH3CN (Prior Art Document 3), the economical efficiency is lowered because expensive N-bromosuccinimide is used in the progress of the bromination reaction. In addition, there is a bromination reaction using K 2 S 2 O 8 and KBr (Prior Art 4), but the time required to complete the reaction is as long as 12 hours and heat must be applied during the reaction. Also, the method of directly using bromine (Br 2 ) in the conventional bromination reaction (prior art 5) is difficult to ensure the safety of the operator and requires considerable care in handling and avoids application to the production process. On the other hand, when N-bromosuccinimide (NBS) is used, economic efficiency is lowered as a main cause of increase in raw material value.
이에 본 발명자들은 브롬산과 산화제를 이용한 새로운 반응 루트를 통하여 브로민의 합성법을 개발하여 본 발명을 완성하기에 이르렀다.
Accordingly, the present inventors have completed the present invention by developing a synthesis method of bromine through a novel reaction route using bromic acid and an oxidizing agent.
본 발명의 목적은 환경친화적이고 경제적인 페닐 알킬 케톤 유도체의 α-브로민화 방법을 제공하는 것이다.
It is an object of the present invention to provide a process for the? -Bromination of an environmentally friendly and economical phenylalkylketone derivative.
상기 목적을 달성하기 위해 본 발명은, In order to achieve the above object,
1) 브로민화 수소산 수용액에 산화제를 첨가 및 교반하여 브로민을 합성하는 단계; 및 2) 페닐 알킬 케톤 유도체를 출발물질로 하여, 상기 1) 단계의 브로민화 반응을 이용해 페닐 알킬 α-브로모 케톤 유도체를 합성하는 단계; 를 포함하는 페닐 알킬 케톤 유도체의 α-브로민화 방법을 제공한다. 1) adding an oxidizing agent to an aqueous solution of hydrobromic acid and stirring to synthesize bromine; And 2) synthesizing a phenylalkyl? -Bromo ketone derivative using the phenylalkyl ketone derivative as a starting material, using the bromination reaction in the step 1); ≪ RTI ID = 0.0 > a < / RTI > phenylalkyl ketone derivative.
본 발명은 또한, The present invention also relates to
1) 페닐 알킬 케톤 유도체에 브로민화 수소산 수용액을 첨가하고 교반하는 단계; 및2) 산화제를 첨가하고 교반하여 페닐 알킬 α-브로모 케톤 유도체를 합성하는 단계; 를 포함하는 페닐 알킬 케톤 유도체의 친환경 α-브로민화 방법을 제공한다.
1) adding an aqueous solution of hydrobromic acid to a phenylalkylketone derivative and stirring the mixture; And 2) adding an oxidizing agent and stirring to synthesize a phenylalkyl? -Bromo ketone derivative; A method for environmental a-bromination of a phenylalkylketone derivative comprising
브로민 작용기는 후기단계 반응을 위한 전구물질 합성을 위해 널리 사용되고 있다. 그러나 브로민(Br2)을 직접 사용하는 일반적인 브로민화 반응은 작업과정이 위험하고 폐수 등의 부산물의 발생으로 폐화합물 처리를 위한 추가적 비용이 들고, 환경오염이 발생된다. 본 발명의 방법은 이에 따라 브로민화 반응을 한 후, 생성되는 HBr을 다시 산화시켜 브로민을 생성하는 원리로, 부산물이 없고 생산 효율이 높은 방법을 제공한다. Bromine functional groups are widely used for the synthesis of precursors for later stage reactions. However, the general bromination reaction using bromine (Br 2 ) is dangerous in the work process, and the byproducts such as wastewater are generated, resulting in additional costs for disposal of waste compounds and environmental pollution. The method of the present invention is a principle of producing bromine by carrying out a bromination reaction and then oxidizing the generated HBr again, thereby providing a process without any byproducts and having a high production efficiency.
본 발명의 α-브로민화 방법은 이에 제한되는 것은 아니나, 바람직하게 하기 반응식 1로 나타낼 수 있다.The? -Bromination method of the present invention is not limited thereto, but can be preferably represented by the following reaction formula (1).
[반응식 1][Reaction Scheme 1]
본 발명의 방법에서 먼저 브로민의 합성단계는 브로민화 수소산(HBr) 수용액에 산화제를 첨가 및 교반하여 브로민을 합성하는 것일 수 있다. In the method of the present invention, the step of synthesizing bromine may be performed by adding an oxidizing agent to an aqueous solution of hydrobromic acid (HBr) and stirring to synthesize bromine.
본 발명의 구체예에서, 상기 산화제는 바람직하게 염소산나트륨일 수 있으나 이에 제한되는 것은 아니다. In an embodiment of the present invention, the oxidizing agent is preferably, but not limited to, sodium chlorate.
본 발명에서 브로민을 생성하는 반응식은 다음과 같다.The reaction formula for producing bromine in the present invention is as follows.
[반응식 2][Reaction Scheme 2]
NaClO3 +6HBr -> 3Br2 + NaCl + 3H2O NaClO 3 + 6HBr -> 3Br 2 + NaCl + 3H 2 O
본 발명의 구체예에서, 상기 브로민화 생성 반응 이후, 생성되는 HBr을 다시 산화시켜 브로민을 재생할 수 있다. 따라서 반응 완결 후 남아있는 HBr은 없다. In an embodiment of the present invention, after the bromination reaction, bromine can be regenerated by reoxidizing the HBr produced. Therefore, there is no residual HBr after completion of the reaction.
상기 페닐 알킬 케톤 유도체, 브로민화 수소산 수용액 및 산화제의 중량비는 이에 제한되는 것은 아니나 바람직하게 1: 1~2: 0.2~0.8, 특히 1: 1~2: 0.4~0.8일 수 있다. 상기 범위를 벗어나는 경우, 과량의 브로민이 생성되거나, 페닐 알킬 케톤 유도체의 브로민화가 진행되지 않을 수 있다.The weight ratio of the phenylalkylketone derivative, the aqueous solution of hydrobromic acid and the oxidizing agent may be 1: 1 to 2: 0.2 to 0.8, especially 1: 1 to 2: 0.4 to 0.8. Exceeding the above range, excessive bromine may be produced, or the bromination of the phenylalkylketone derivative may not proceed.
본 발명의 구체예에서, 상기 산화제는 고체 또는 수용액 형태일 수 있으나 이에 제한되는 것은 아니다. In embodiments of the present invention, the oxidant may be in the form of a solid or aqueous solution, but is not limited thereto.
상기 페닐 알킬 케톤 유도체는 이에 제한되는 것은 아니나 바람직하게 하기 화학식 1로 표시되는 화합물일 수 있다.The phenylalkylketone derivative may be a compound represented by the following general formula (1), but is not limited thereto.
[화학식 1][Chemical Formula 1]
(상기 화학식 1에서 R1은 수소, 치환 또는 비치환된 C1~C25의 알킬기, 치환 또는 비치환된 C2~C25의 알케닐기, 치환 또는 비치환된 C1~C25의 알콕시기, 치환 또는 비치환된 C6~C30의 아릴기, 치환 또는 비치환된 C5~C25의 헤테로아릴기 또는 할로겐이고, R2는 치환 또는 비치환된 C1~C25의 알킬기, 치환 또는 비치환된 C2~C25의 알케닐기, 치환 또는 비치환된 C1~C25의 알콕시기, 치환 또는 비치환된 C6~C30의 아릴기 또는 치환 또는 비치환된 C5~C25의 헤테로아릴기이다.)
(Wherein R1 is hydrogen, a substituted or unsubstituted C1 to C25 alkyl group, a substituted or unsubstituted C2 to C25 alkenyl group, a substituted or unsubstituted C1 to C25 alkoxy group, a substituted or unsubstituted C6 A substituted or unsubstituted C5 to C25 heteroaryl group or a halogen; R2 is a substituted or unsubstituted C1 to C25 alkyl group, a substituted or unsubstituted C2 to C25 alkenyl group, a substituted or unsubstituted C5 to C25 heteroaryl group, A substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted C5-C25 heteroaryl group.
본 발명의 구체예에서는, 브로민화 수소산에 염소산나트륨을 투입하여 교반시킴으로써 브로민을 생성하였으며, 프로피오페논(propiophenone, 1-phenyl-1-propanone)을 출발물질로 하여 브로민화 반응을 진행함으로써 α-브로모 프로피오페논을 합성하였다. 본 발명의 상기 방법은 브로민의 재생이 가능하므로, HBr 1당량을 사용(당량 최소화)하더라도 순환에 의해 부산물이 생성되지 않아 효율적이고, 반응 수율이 높은 효과가 있다. 또한 선택적으로 α-브로민화가 가능하다. 또한 생성된 α-브로모 프로피오페논을 이용하여, 2-(Methylamino)ethanol (MEA)의 치환반응을 이용해 3,4-dimethyl-2-phenyl-2-morpholinol(DPM)의 합성이 가능하다. 이와 같이 본 발명의 브로민화 반응을 의약 원제의 합성과정에 사용할 수 있다. 따라서 기존 합성법에 비해 고가 또는 다루기 어려운 화학물질의 대체가 가능하며, 반응 완결 후 발생하는 폐화합물의 양을 감소시켜 환경 친화적이고 경제적인 합성이 가능하다.
In an embodiment of the present invention, bromine was produced by adding sodium chlorate to hydrobromic acid and stirring, and bromination reaction was carried out using propiophenone (1-phenyl-1-propanone) as a starting material, -Bromopropiophenone was synthesized. Since the bromine can be regenerated by the method of the present invention, by-products can not be produced by circulation even when 1 equivalent of HBr is used (equivalent amount is minimized), which is effective, and the reaction yield is high. Also alpha -bromination is possible. It is also possible to synthesize 3,4-dimethyl-2-phenyl-2-morpholinol (DPM) by substitution reaction of 2- (methylamino) ethanol (MEA) using the produced α-bromopropionone. Thus, the bromination reaction of the present invention can be used in the synthesis of the pharmaceutical preparation. Therefore, it is possible to substitute chemicals which are expensive or difficult to handle compared with the conventional synthesis method, and it is possible to synthesize environmentally friendly and economical by reducing the amount of waste compounds generated after completion of the reaction.
다른 식으로 정의되지 않는 한, 본 명세서에서 사용된 모든 기술적 및 과학적 용어들은 본 발명이 속하는 기술분야에서 숙련된 전문가에 의해서 통상적으로 이해되는 것과 동일한 의미를 갖는다. 일반적으로, 본 명세서에서 사용된 명명법은 본 기술분야에서 잘 알려져 있고 통상적으로 사용되는 것이다.
Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In general, the nomenclature used herein is well known and commonly used in the art.
본 발명의 브로민화 반응은 1당량의 브로민화 수소(HBr)를 사용하더라도 브로민의 생성 이후, HBr을 모두 소진하는바, 부산물의 생성이 없어 환경 친화적이다. 또한 반응시간이 1시간 이내로 반응 효율이 높고 일정하게 유지되며, 선택적인 반응이 가능하다.
The bromination reaction of the present invention is environmentally friendly because it produces no bromine since HBr is exhausted after the production of bromine even when one equivalent of hydrogen bromide (HBr) is used. In addition, the reaction efficiency is maintained high and constant within 1 hour, and selective reaction is possible.
도 1은 α-브로모 프로피오페논의 1H NMR Spectrum 스펙트럼이다. 1 is a 1 H NMR Spectrum spectrum of? -Bromopropiophenone.
이하, 실시예를 통하여 본 발명을 더욱 상세히 설명하고자 한다. 이들 실시예는 오로지 본 발명을 예시하기 위한 것으로서, 본 발명의 범위가 이들 실시예에 의해 제한되는 것으로 해석되지는 않는 것은 이 기술분야에서 통상의 지식을 가진 자에게 있어서 자명할 것이다.
Hereinafter, the present invention will be described in more detail with reference to Examples. It is to be understood by those skilled in the art that these embodiments are merely illustrative of the present invention and that the scope of the present invention is not construed as being limited by these embodiments.
실시예Example 1: α- 1: α- 브로모Bromo 프로피오페논의Propiophenone 제조 Produce
프로피오페논 5mL에 48w% 브로민화 수소산(Hydrobromic acid) 4.9mL를 투입하고 교반하였다. 이후, 5M 염소산 나트륨(sodium chlorate) 3mL를 10분간 천천히 투입하고, 상기 혼합물을 30분동안 교반시켰다. 반응이 끝난 후, 티오황산 나트륨(sodium thiosulfate) 1.6mL를 투입하여 브로민(bromine)을 제거하였다. 이후, 메틸렌 클로라이드(Methylene chloride) 20mL와 브라인 용액(brine solution) 20mL를 첨가한 후, 흔들고 물층과 메틸렌 클로라이드층을 분리하였다. 그리고, 물 층에 생성물이 남아있지 않을 때까지 추출하였다(20mL x 3번). 그 후, 메틸렌 클로라이드 층을 분리하여 MgSO4로 물을 제거한 후 감압여과하고, 이베포레이션(Evaporation)으로 메틸렌 클로라이드를 증발시켰다. 진공 건조 후 노란빛을 띄는 목적 화합물인 α-브로모 프로피오페논 7.8g (crude yield 98%)을 얻었다(도 1).
To 5 mL of propiophenone, 4.9 mL of 48 wt% hydrobromic acid was added and stirred. Then, 3 mL of 5 M sodium chlorate was slowly added for 10 minutes, and the mixture was stirred for 30 minutes. After the reaction was completed, 1.6 mL of sodium thiosulfate was added to remove bromine. Then, 20 mL of methylene chloride and 20 mL of brine solution were added, and the mixture was shaken to separate the water layer and the methylene chloride layer. Then, the solution was extracted (20 mL x 3 times) until no product remained in the water layer. Thereafter, the methylene chloride layer was separated, water was removed with MgSO 4 , filtered under reduced pressure, and methylene chloride was evaporated by evaporation. After vacuum drying, 7.8 g (crude yield: 98%) of [alpha] -bromopropiophenone as a yellowish target compound was obtained (Fig. 1).
실시예Example 1-1: 1-1: KClOKClO 33 첨가를 통해 생성된 ≪ RTI ID = 0.0 > 브로민을Bromine 이용한 α- The α- 브로민화Bromination 반응 reaction
고체(Solid) 형태로 염소산칼륨(KClO3)를 첨가하였다. 첨가조건은 하기 표 1과 같다. Potassium chlorate (KClO 3 ) was added in solid form. The addition conditions are shown in Table 1 below.
실험 결과, 고체 형태로 KClO3를 첨가한 경우, 발생하는 Br2 가스로 인해 문제가 될 수 있어, KClO3를 수용액 형태로 첨가하였다. 첨가 조건은 하기 표 2와 같다. Experimental results show that the addition of KClO 3 in the solid form can be a problem due to the generated Br 2 gas, and KClO 3 is added in the form of aqueous solution. The addition conditions are shown in Table 2 below.
수용액 형태의 KClO3를 산화제로 이용한 경우, KClO3의 물에 대한 용해도가 낮아 반응성이 떨어지는 것을 확인할 수 있었다. 이에 따라 용해도 문제를 해결하기 위해, 염소산 나트륨(NaClO3)을 사용하였다.
When KClO 3 in the form of aqueous solution was used as an oxidizing agent, the solubility of KClO 3 in water was low, indicating that the reactivity was inferior. Accordingly, sodium chlorate (NaClO 3 ) was used to solve the problem of solubility.
실시예Example 1-2: 1-2: NaClONaClO 33 첨가를 통해 생성된 ≪ RTI ID = 0.0 > 브로민을Bromine 이용한 α- The α- 브로민화Bromination 반응 reaction
고체(Solid) 및 수용액 형태로 염소산나트륨(NaClO3)를 첨가하였다. 첨가조건은 하기 표 3 및 표 4와 같다. Sodium chlorate (NaClO 3 ) was added in solid and aqueous form. The addition conditions are shown in Tables 3 and 4 below.
염소산나트륨의 경우, 용해도가 105.7g/100mL (25℃) 로 KClO3 용해도 8.15g/100mL (25℃)보다 높아 수용액의 형태로 첨가가 가능하다. 따라서 생성되는 부산물이 없이 친환경적인 브로민화가 가능한 것을 확인하였다. 반응 결과, 프로피오페논: 브로민화 수소산: 염소산나트륨의 최적 중량비는 1:1.1:0.4로 나타났다. 또한 시간도 0.5 내지 1시간으로 단축되어 적은 비용으로 높은 효율의 반응이 가능하였다.
In the case of sodium chlorate, the solubility is 105.7 g / 100 mL (25 ° C.) and the KClO 3 solubility is higher than 8.15 g / 100 mL (25 ° C.). Therefore, it was confirmed that environmentally friendly bromination was possible without any byproducts generated. As a result of the reaction, the optimum weight ratio of propiophenone: hydrobromic acid: sodium chlorate was 1: 1.1: 0.4. In addition, the time was shortened to 0.5 to 1 hour, and a high efficiency reaction was possible at a low cost.
목적물질로 수득된 화합물에 대하여 핵자기 공명(NMR) 데이터를 분석한 결과를 도 1로 나타내었다. 이 때 핵자기 공명(NMR)의 측정조건은 다음과 같다.The results obtained by analyzing nuclear magnetic resonance (NMR) data of the compound obtained as a target substance are shown in Fig. The measurement conditions of nuclear magnetic resonance (NMR) at this time are as follows.
1. 장치 : 핵자기 공명 스펙트럼 분석( 장치 : Bruker 400MHz)1. Apparatus: Nuclear magnetic resonance spectrum analysis (apparatus: Bruker 400 MHz)
2. 측정범위 : -0.5 ~ 10.5ppm (1H); 2. Measuring range: -0.5 ~ 10.5ppm (1H);
3. 스캔 횟수 : 16 (1H)3. Number of scans: 16 (1H)
Claims (5)
2) 상기 1) 단계에서 합성된 브로민과 하기 화학식 1로 나타내는 페닐 알킬 케톤 유도체를 반응시켜 하기 화학식 2로 나타내는 페닐 알킬 α-브로모 케톤 유도체를 합성하는 단계;를 포함하고,
페닐 알킬 케톤 유도체, 브로민화 수소산 수용액 및 염소산 나트륨의 중량비는 1 : 1~2 : 0.4~0.8이며,
반응시간은 0.5 내지 1시간인 것을 특징으로 하는 페닐 알킬 케톤 유도체의 친환경 α-브로민화 방법.
[반응식 1]
(상기 반응식 1에서,
R1은 수소이고,
R2는 치환 또는 비치환된 C1~C25의 알킬기이다.)
1) adding sodium chlorate to an aqueous solution of hydrobromic acid and stirring to synthesize bromine; And
2) reacting the bromine synthesized in the above step 1) with a phenylalkylketone derivative represented by the following formula (1) to synthesize a phenylalkyl? -Bromoketone derivative represented by the following formula (2)
The weight ratio of the phenylalkyl ketone derivative, aqueous hydrobromic acid solution and sodium chlorate is 1: 1 to 2: 0.4 to 0.8,
And the reaction time is 0.5 to 1 hour. ≪ RTI ID = 0.0 > 8. < / RTI >
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
R1 is hydrogen,
And R2 is a substituted or unsubstituted C1 to C25 alkyl group.)
2) 염소산나트륨을 첨가하고 교반하여 하기 화학식 2로 나타내는 페닐 알킬 α-브로모 케톤 유도체를 합성하는 단계;를 포함하고,
페닐 알킬 케톤 유도체, 브로민화 수소산 수용액 및 염소산 나트륨의 중량비는 1 : 1~2 : 0.4~0.8이며,
반응시간은 0.5 내지 1시간인 것을 특징으로 하는 페닐 알킬 케톤 유도체의 친환경 α-브로민화 방법.
[반응식 1]
(상기 반응식 1에서,
R1은 수소이고,
R2는 치환 또는 비치환된 C1~C25의 알킬기이다.)
1) adding an aqueous solution of hydrobromic acid to a phenylalkylketone derivative represented by the following formula (1) and stirring; And
2) adding sodium chlorate and stirring to synthesize a phenylalkyl? -Bromoketone derivative represented by the following formula 2,
The weight ratio of the phenylalkyl ketone derivative, aqueous hydrobromic acid solution and sodium chlorate is 1: 1 to 2: 0.4 to 0.8,
And the reaction time is 0.5 to 1 hour. ≪ RTI ID = 0.0 > 8. < / RTI >
[Reaction Scheme 1]
(In the above Reaction Scheme 1,
R1 is hydrogen,
And R2 is a substituted or unsubstituted C1 to C25 alkyl group.)
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| Bull. Korean Chem. Soc., Vol.32, pp.472-476 (2011) |
| Green Chem., Vol.9, pp.1212-1218 (2007)* |
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