KR20090038270A - A method for preparing thiomethylphenols - Google Patents
A method for preparing thiomethylphenols Download PDFInfo
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- KR20090038270A KR20090038270A KR1020070103681A KR20070103681A KR20090038270A KR 20090038270 A KR20090038270 A KR 20090038270A KR 1020070103681 A KR1020070103681 A KR 1020070103681A KR 20070103681 A KR20070103681 A KR 20070103681A KR 20090038270 A KR20090038270 A KR 20090038270A
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- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
- C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
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- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
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- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
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Abstract
Description
본 발명은 티오메틸페놀 유도체의 제조방법에 관한 것으로서, 더욱 상세하게는 직쇄형 아민의 염기와 동시에 산이 일정량 존재하는 조건하에서 페놀 유도체, 메르캅탄 유도체 및 파라포름알데히드를 용매중에서 반응을 수행하는 손쉬운 공정으로, 종래에 비해 온화한 반응조건을 갖는 티오메틸페놀 유도체의 제조방법에 관한 것이다.The present invention relates to a method for preparing a thiomethylphenol derivative, and more particularly, an easy process for carrying out a reaction of a phenol derivative, a mercaptan derivative, and paraformaldehyde in a solvent under conditions in which a certain amount of acid is present simultaneously with a base of a linear amine. The present invention relates to a method for producing a thiomethylphenol derivative having milder reaction conditions than in the prior art.
티오메틸페놀은 플라스틱, 엘라스트로머, 미네랄오일, 합성오일에 중요한 산화방지제로 널리 사용되고 있다.Thiomethylphenol is widely used as an important antioxidant in plastics, elastomers, mineral oils and synthetic oils.
티오메틸페놀 유도체를 제조하는 방법을 구체적으로 살펴보면 다음과 같다. 2-(디메틸아미노메틸)-4-메틸페놀을 티오아세트 산 S-에틸에스터와 반응시켜 티오메틸페놀 유도체를 제조하는 것이 미국특허 제4,091,037호에 기술되어 있다. Zn(OAc)2 존재하에 페놀, 파라포름알데히드, 메르캅탄 유도체와 반응시켜 티오메틸페놀 유도체를 제조하는 것이 미국특허 제4,304,940호에 기술되어 있다. 또한, 모노-, 디, 또는 트리메틸아민 또는 모노- 또는 디에틸아민과 같은 염기와 N,N-디메틸포름아미드 같은 용매 존재하에 155 ℃에서 2시간동안 포름알데히드 및 메르캅탄 유도체와 반응에 의해 티오메틸페놀 유도체의 황색 액체를 제조하는 것이 한국특허공고 제1995-9748호와 미국특허 제4,874,885호에 기술되어 있다. Looking at the method for producing a thiomethylphenol derivative in detail. The preparation of thiomethylphenol derivatives by reacting 2- (dimethylaminomethyl) -4-methylphenol with thioacetic acid S-ethylester is described in US Pat. No. 4,091,037. The preparation of thiomethylphenol derivatives by reaction with phenol, paraformaldehyde, mercaptan derivatives in the presence of Zn (OAc) 2 is described in US Pat. No. 4,304,940. In addition, thiomethyl was reacted with formaldehyde and mercaptan derivatives at 155 ° C. for 2 hours in the presence of a base such as mono-, di, or trimethylamine or mono- or diethylamine and a solvent such as N, N- dimethylformamide. The preparation of yellow liquids of phenol derivatives is described in Korean Patent Publication Nos. 1995-9748 and 4,874,885.
이외에도 모노, 디, 또는 트리메틸아민이나 모노 또는 디에틸아민과 같은 염기 존재하에 용매없이 130 ℃에서 3.5시간동안 포름알데히드 및 메르캅탄 유도체와 반응한 후 반응생성물을 90 ℃에서 7시간동안 환원제로 처리하여 티오메틸페놀 유도체를 제조, 정제하는 것이 한국특허공개 제2001-0000988호와 미국특허 제6,365,781호에 기술되어 있다. 이때, 촉매는 단지 모노-, 또는 디메틸아민, 또는 모노- 또는 디에틸아민 등의 염기만을 사용하고 있다. In addition, the reaction product was reacted with formaldehyde and mercaptan derivatives at 130 ° C. for 3.5 hours without solvent in the presence of a base such as mono, di, or trimethylamine or mono or diethylamine, and then the reaction product was treated with a reducing agent at 90 ° C. for 7 hours. The preparation and purification of thiomethylphenol derivatives is described in Korean Patent Publication No. 2001-0000988 and US Patent No. 6,365,781. At this time, the catalyst uses only a base such as mono- or dimethylamine or mono- or diethylamine.
그러나, 상기와 같은 제조방법은 반응온도가 높고 반응시간이 긴 제조방법상의 문제와 더불어, 염기만을 사용하는 경우, 염기에 의한 페논(phenone)이 형성함으로써 제품의 변색이 발생한다. 이러한 변색을 해결하고자 환원제인 NaBH4로 페논을 페놀로 환원시키는 정제방법을 사용하고 있다. 이와 같이, 티오메틸페놀 유도체를 정제한다하더라도 정제시간이 길고, 반응 및 정제하는 과정에서 염기의 산화에 의해 변색이 발생하는 문제점을 가지고 있다. However, the manufacturing method as described above has a problem in the manufacturing method with a high reaction temperature and a long reaction time, and when only the base is used, discoloration of the product occurs due to the formation of phenone by the base. In order to solve such discoloration, a purification method of reducing phenone to phenol with NaBH 4 as a reducing agent is used. As described above, even when the thiomethylphenol derivative is purified, the purification time is long, and there is a problem that discoloration occurs due to oxidation of the base during the reaction and purification.
이에 본 발명자들은 종래 티오메틸페놀의 제조에 요구되는 혹독한 반응조건을 개선하고자 연구 노력하였다. 그 결과, 직쇄형 아민의 염기(base)와 산(acid)이 동시에 존재하는 조건하에서, 페놀 유도체, 메르캅탄 유도체 및 파라포름알데히드를 용매중에서 반응을 수행하여 티오메틸페놀 유도체를 제조하면, 상기 직쇄형 아민의 염기만의 사용으로 온도가 상승하여 제조되는 반응생성물의 변색을 억제하는 동시에 용매하에서 반응이 수행되어 반응속도가 상승된다는 것을 알게 되었다.The present inventors have tried to improve the harsh reaction conditions required for the preparation of conventional thiomethylphenol. As a result, thiomethylphenol derivative is prepared by reacting a phenol derivative, a mercaptan derivative and a paraformaldehyde in a solvent under conditions in which both a base and an acid of a linear amine are present at the same time. It was found that the reaction rate was increased by inhibiting discoloration of the reaction product produced by increasing the temperature by using only the base of the chained amine, while increasing the reaction rate in the solvent.
또한, 상기 염기와 파라포름알데히드로부터 1차로 생성된 중간체인 아미노메탄올이 염기와 동시에 첨가되는 산에 의해 반응성이 매우 큰 이민으로 전환되어 페놀과의 반응성을 극대화시킴으로써 반응조건이 중간체인 아미노메탄올의 페놀과의 반응보다 온화하게 된다는 것을 알게 되어 본 발명을 완성하게 되었다.In addition, aminomethanol, an intermediate produced primarily from the base and paraformaldehyde, is converted to imine which is highly reactive by an acid added at the same time as the base, thereby maximizing the reactivity with phenol. It was found that the reaction was milder than the reaction with, thus completing the present invention.
본 발명은 직쇄형 아민의 염기(base)와 산(acid)이 동시에 존재하는 조건하에서, 다음 화학식 2로 표시되는 페놀 유도체, R2SH로 표시되는 메르캅탄 유도체, 및 파라포름알데히드를 용매하에서 반응을 수행하여 반응생성물을 얻고 상기반응생성물을 염기 1 당량에 대하여, 산(acid)을 1 ∼ 50 당량 범위로 사용하여 정제하는 것을 특징으로 하는 다음 화학식 1로 표시되는 티오메틸페놀 유도체의 제조방법 에 그 특징이 있다.The present invention reacts a phenol derivative represented by the following formula (2), a mercaptan derivative represented by R 2 SH, and paraformaldehyde in a solvent under the conditions in which both a base and an acid of a linear amine are present at the same time. To obtain a reaction product, and to prepare the thiomethylphenol derivative represented by the following Chemical Formula 1, characterized in that the reaction product is purified using an acid in the range of 1 to 50 equivalents based on 1 equivalent of the base. It has its features.
상기 화학식 1 및 2에서, R1 는 수소원자, 또는 C1 ∼ C16의 직쇄 또는 분쇄 알킬기, 방향족을 포함하는 알킬기, R2는 C1 ∼ C16의 직쇄 또는 분쇄 알킬기, 방향족을 포함하는 알킬기를 나타내고, X은 H, -(CH2)n-, -CMe2-, -Y-를 나타내고, 이때, Y는 벤젠, 비페닐, 톨루엔, 나프탈렌의 방향족 화합물 또는 1개 이상의 알킬기로 치환된 방향족 화합물을 나타내고, n은 0 또는 1 ∼ 8의 정수이고, m은 0 또는 1을 나타낸다.In Chemical Formulas 1 and 2, R 1 is a hydrogen atom, or a C 1 to C 16 straight or crushed alkyl group, an alkyl group containing an aromatic, R 2 is a C 1 to C 16 straight or crushed alkyl group, an alkyl group containing an aromatic X represents H,-(CH 2 ) n- , -CMe 2- , -Y-, wherein Y represents an aromatic compound of benzene, biphenyl, toluene, naphthalene or an aromatic substituted with one or more alkyl groups A compound is represented, n is 0 or an integer of 1-8, m shows 0 or 1.
본 발명은 직쇄형 아민의 염기, 산 및 반응용매가 동시에 적용된 조건하에서 티오메틸페놀 유도체를 제조하여, 종래에 비해 반응성이 탁월하여 반응시간과 반응 온도 등의 반응조건이 온화한 조건에서도 반응속도가 증가되어 수율 및 전환율이 우수하다.In the present invention, the thiomethylphenol derivative is prepared under the conditions in which the base, acid, and reaction solvent of the linear amine are simultaneously applied, and the reaction rate is increased even under mild conditions such as reaction time and reaction temperature due to excellent reactivity. The yield and conversion rate are excellent.
본 발명은 직쇄형 아민의 염기(base)와 산(acid)이 동시에 존재하는 조건하에서 페놀 유도체, 메르캅탄 유도체 및 파라포름알데히드를 용매하에서 반응시켜, 종래보다 온화한 조건하에서 전환율, 순도가 우수하고 변색성이 저하된 티오메틸페놀 유도체를 제조하는 방법에 관한 것이다. The present invention reacts phenol derivatives, mercaptan derivatives, and paraformaldehyde in a solvent under conditions in which both a base and an acid of a linear amine are present at the same time, so that conversion, purity and discoloration are excellent under milder conditions than before. The present invention relates to a method for producing a thiomethylphenol derivative having reduced properties.
또한, 본 발명은 극성용매를 사용함으로써 염기와 파라포름알데히드의 반응성을 위한 반응활성화에너지를 낮춤으로써 반응속도를 증가시키는 데 그 특징이 있다.In addition, the present invention is characterized by increasing the reaction rate by lowering the reaction activation energy for the reactivity of the base and paraformaldehyde by using a polar solvent.
또한, 본 발명은 상기 산이 첨가되어 염기와 파라포름알데히드로부터 1 차로 생성된 중간체인 아미노메탄올이 산에 의해 반응성이 매우 큰 이민으로 전환되어 페놀과의 반응성을 극대화시킴으로써 반응조건이 중간체인 아미노메탄올의 페놀과의 반응보다 온화한 조건을 유지할 뿐만 아니라 염기의 산화를 방지해줌으로써 반응 시 일어나는 변색을 억제하는 데 특징이 있다.In addition, the present invention is the addition of the acid to the amino-methanol, the intermediate produced primarily from the base and paraformaldehyde is converted to imine with a very high reactivity by the acid to maximize the reactivity with phenol to the reaction conditions of the intermediate aminomethanol In addition to maintaining milder conditions than the reaction with phenol, it is characterized by suppressing discoloration during the reaction by preventing oxidation of the base.
본 발명에 따른 티오메틸페놀 유도체를 제조하는 방법을 보다 구체적으로 살펴보면 다음과 같다.Looking at the method for producing a thiomethylphenol derivative according to the present invention in more detail.
본 발명은 탄소수 4 ∼ 10의 직쇄형 아민의 염기의 염기(base)와 산(acid)이 동시에 존재하는 조건하에서, 상기 화학식 2로 표시되는 페놀 유도체, R2SH로 표시되는 메르캅탄 유도체, 및 파라포름알데히드를 용매하에서 반응을 수행한다.The present invention provides a phenol derivative represented by the formula (2), a mercaptan derivative represented by R 2 SH, under the condition that both a base and an acid of a base of a linear amine having 4 to 10 carbon atoms are present at the same time; Paraformaldehyde is carried out in a solvent.
상기 반응의 원료로 사용되는 상기 화학식 1로 표시되는 페놀 유도체, 메르캅탄 유도체 및 파라포름알데히드는 당 분야에서 일반적으로 사용되는 것으로 특별히 한정하지는 않으며, 구체적으로, 페놀 유도체는 o-크레졸, p-크레졸, 4-부틸페놀 및 비스페놀 등이 사용될 수 있고, 메르캅탄 유도체는 옥탄메르캅탄, 데칸메르캅탄, 도데칸메르캅탄, 벤질메르캅탄 등이 사용될 수 있다.Phenolic derivatives, mercaptan derivatives and paraformaldehyde represented by Formula 1 used as raw materials for the reaction are not particularly limited to those commonly used in the art, and specifically, phenol derivatives are o-cresol and p-cresol. , 4-butylphenol and bisphenol may be used, and mercaptan derivatives may include octane mercaptan, decane mercaptan, dodecan mercaptan, benzyl mercaptan, and the like.
상기 반응원료는 상기 화학식 1로 표시되는 티오메틸페놀 유도체를 형성할 수 있는 당량비로 사용하는 바, 구체적으로 페놀 유도체 1 당량에 대하여 파라포름알데히드 2 ∼ 3 당량범위, 바람직하기로는 2 ∼ 2.5 당량범위로 사용하고, 메르캅탄 유도체는 2 ∼ 3 당량범위, 바람직하기로는 2 ∼ 2.5 당량범위로 사용할 수 있다. 상기 파라포름알데히드의 사용량이 2 당량 미만이면 미반응으로 인해 모노티오메틸페놀과 디티오메틸페놀의 혼합물이 생성되고 3 당량을 초과하는 경우에는 정제시간이 길어지는 문제가 발생하고, 메르캅탄 유도체의 사용량이 2 당량 미만이면 미반응으로 인해 모노티오메틸페놀과 디티오메틸페놀의 혼합물이 생성되고 3 당량을 초과하는 경우에는 부산물이 많아지고 정제시간이 길어지는 문제가 발생한다.The reaction raw material is used in an equivalent ratio capable of forming a thiomethylphenol derivative represented by Chemical Formula 1, specifically, 2 to 3 equivalents of paraformaldehyde, preferably 2 to 2.5 equivalents, based on 1 equivalent of the phenol derivative. The mercaptan derivative may be used in the range of 2 to 3 equivalents, preferably in the range of 2 to 2.5 equivalents. If the amount of paraformaldehyde is less than 2 equivalents, a mixture of monothiomethylphenol and dithiomethylphenol is generated due to unreacted reaction, and when the amount exceeds 3 equivalents, the purification time is long. If the amount is less than 2 equivalents, a mixture of monothiomethyl phenol and dithiomethyl phenol is produced due to unreacted reaction. If the amount is more than 3 equivalents, there is a problem of increasing by-products and lengthening purification time.
상기 염기로 사용되는 헤테로 고리형 아민은 당 분야에서 일반적으로 사용되는 것으로 특별히 한정하지는 않으나, 탄소수 4 ∼ 10을 갖는 직쇄형 아민, 구체적으로 디메틸아민, 디에틸아민, 벤질메틸아민 중에서 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있다. 이러한 직쇄형 아민은 페놀 유도체 1 당량에 대하여 0.05 ∼ 0.5 당량 범위, 바람직하기로는 0.1 ∼ 0.3 범위로 사용하는 바, 상기 사용량이 0.05 당량 미만이면 반응시간이 길어지고 0.5 당량을 초과하는 경우에는 반응시간이 짧아지나 부산물이 많아지는 문제가 발생하므로 상기 범위를 유지하는 것이 바람직하다.The heterocyclic amine used as the base is generally used in the art, and is not particularly limited, but is a linear amine having 4 to 10 carbon atoms, specifically, one selected from dimethylamine, diethylamine, and benzylmethylamine. Mixtures of two or more may be used. The linear amine is used in the range of 0.05 to 0.5 equivalents, preferably in the range of 0.1 to 0.3, based on 1 equivalent of the phenol derivative. When the amount is less than 0.05 equivalent, the reaction time is long and the reaction time is greater than 0.5 equivalent. It is preferable to keep the above range because the problem of shortening or by-products increases.
또한, 본 발명에서 상기 직쇄형 아민의 염기와 동시에 사용되는 산은 유기산 및 무기산 중에서 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있다. 구체적으로 상기 유기산은 카르복실산, 황산, 인산 중에서 선택된 작용기를 갖는 지방족 및 방향족 유기산을 단독으로 사용하거나, 또는 알킬기(alkyl), 알케닐기(alkenyl), 아릴기(aryl), 하이드록시기, 티올기, 아민기, 에테르기, 에스터기, 아미드기, 케톤기, 알데히드기, 에테르기, 카르복실기, 설폰기, 인산기 중에서 선택된 1종 또는 2종 이상의 기능기와 카르복실산, 황산, 인산 중에서 선택된 작용기를 동시에 갖는 지방족 및 방향족 유기산을 사용할 수 있다.In addition, the acid used simultaneously with the base of the linear amine in the present invention may be used one or a mixture of two or more selected from organic acids and inorganic acids. Specifically, the organic acid may be used alone with an aliphatic and aromatic organic acid having a functional group selected from carboxylic acid, sulfuric acid, phosphoric acid, or an alkyl group, alkenyl group, aryl group, hydroxy group, thiol At least one functional group selected from a group, an amine group, an ether group, an ester group, an amide group, a ketone group, an aldehyde group, an ether group, a carboxyl group, a sulfone group and a phosphoric acid group and a functional group selected from a carboxylic acid, sulfuric acid or phosphoric acid It is possible to use aliphatic and aromatic organic acids having.
상기 무기산은 H2CO3, H2SO4, H3PO4 등의 하나를 사용하거나 또는 두 개 이상의 산소 산으로 구성된 복합 무기산의 헤테로 산을 사용할 수 있다. 이때, 두 개 이상의 산소 산으로 구성된 복합 무기산의 헤테로 산(heterogenous acid)은 클레이(clay), 양이온교환수지, 실리카-폴리머 등이 사용될 수 있다.The inorganic acid is H 2 CO 3 , H 2 SO 4 , One such as H 3 PO 4 or the like or a hetero acid of a complex inorganic acid composed of two or more oxygen acids can be used. At this time, the hetero acid (heterogenous acid) of the complex inorganic acid composed of two or more oxygen acids may be used (clay), cation exchange resin, silica-polymer and the like.
이러한 반응에 사용되는 산은 염기 1 당량에 대하여 0.01 ∼ 0.9 당량 범위, 바람직하기로는 0.4 ∼ 0.8 당량 범위로 사용하는 바, 사용량이 0.05 당량 미만이 면 산의 효과가 전혀 없고 0.9 당량을 초과하는 경우에는 염기의 역할을 전혀 할 수 없는 문제가 발생하므로 상기 범위를 유지하는 것이 바람직하다.The acid used in this reaction is used in the range of 0.01 to 0.9 equivalents, preferably 0.4 to 0.8 equivalents, based on 1 equivalent of base. If the amount is less than 0.05 equivalent, the acid has no effect and exceeds 0.9 equivalent. It is preferable to maintain the above range because a problem arises in which the base can not be played at all.
이때, 상기 티오메틸페놀 유도체의 제조 시 반응조건은 통상적으로 염기의 종류에 따라 120 ∼ 150 ℃에서 3 ∼ 6 시간동안 수행되나, 본 발명은 특정의 헤테로 고리형 아민은 반응온도가 20 ∼ 60 ℃ 정도 낮아지고 반응시간도 1 ∼ 4 시간 이상 단축되어 종래보다 온화한 조건인 50 ∼ 150 ℃, 바람직하기로는 90 ∼ 120 ℃에서 0.5 ∼ 2.5 시간, 바람직하기로는 1 ∼ 2 시간동안의 범위내에서도 반응의 수행이 가능하다. 상기 반응온도가 50 ℃ 미만이면 반응이 원활하게 수행되지 못하여 미반응이 일어나고, 150 ℃를 초과하는 경우에도 반응이 잘 진행되고 변색도 발생하지 않으나, 경제성이 저하되는 문제가 있다. 또한, 반응시간이 1 시간 미만이면 반응을 위한 충분한 시간이 없어 미 반응이 일어나고 2 시간을 초과하는 경우에도 변색은 발생하지 않으나, 효율성이 떨어지는 문제가 있다.At this time, the reaction conditions in the preparation of the thiomethylphenol derivative is usually carried out for 3 to 6 hours at 120 ~ 150 ℃ depending on the type of base, in the present invention, the specific heterocyclic amine has a reaction temperature of 20 ~ 60 ℃ The reaction time is lowered and the reaction time is shortened by 1 to 4 hours or more, so that the reaction can be carried out within a range of 0.5 to 2.5 hours, preferably 1 to 2 hours at 50 to 150 ° C, preferably 90 to 120 ° C, which is milder than conventional conditions. This is possible. If the reaction temperature is less than 50 ℃ the reaction is not performed smoothly occurs unreacted, even if it exceeds 150 ℃ the reaction proceeds well and does not occur discoloration, there is a problem that economic efficiency is lowered. In addition, if the reaction time is less than 1 hour, there is not enough time for the reaction, even if the unreacted and exceeds 2 hours, but discoloration does not occur, there is a problem that the efficiency is lowered.
상기 반응용매는 물 및 알코올 중에서 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있으며, 알코올은 구체적으로 탄소수 1 ∼ 6의 저급알코올을 사용하는 것이 바람직하다. 이때, 반응용매는 반응 수행에 적합한 범위로 상기 염기 1 당량에 대하여 염기 1 당량에 대하여 0.5 ∼ 50 당량 범위, 바람직하기로는 1 ∼ 20 당량 범위로 사용하는 바, 상기 범위를 벗어나는 경우에는 반응수행 및 반응속도에 문제가 있어 반응성이 떨어지므로 상기 범위를 유지하는 것이 좋다.The reaction solvent may be used one or a mixture of two or more selected from water and alcohol, it is preferable to use a lower alcohol having 1 to 6 carbon atoms specifically. In this case, the reaction solvent is used in the range suitable for carrying out the reaction in the range of 0.5 to 50 equivalents, preferably 1 to 20 equivalents, based on 1 equivalent of the base to 1 equivalent of the base. There is a problem in the reaction rate, so the reactivity is poor, it is good to maintain the above range.
한편, 본 발명에 따라 제조된 티오메틸페놀 유도체의 변색 특성을 효과적으로 제어하기 위하여 정제과정을 수행할 수 있는 바, 이러한 정제과정은 반드시 수 행되는 것이 아니라 필요에 따라 선택 사용할 수 있다. 다음은 정제과정의 일례로 산을 이용한 정제과정을 수행한 경우를 예시한 것이며, 본 발명에 이에 한정되는 것이 아니다.On the other hand, the purification process can be carried out in order to effectively control the discoloration characteristics of the thiomethylphenol derivative prepared according to the present invention, this purification process is not necessarily performed, can be selected and used as needed. The following illustrates an example in which a purification process using an acid is performed as an example of the purification process, and is not limited thereto.
일반적으로 반응과정에서 생성된 중간체인 아미노메탄올이 유기층에 잔류되어 있는 경우, 시간이 경과함에 따라 상기 아미노메탄올이 산화되어 티오메틸페놀 유도체의 변색이 유도된다. 본 발명은 변색에 특히 효과가 있는 정제방법으로 산을 이용한 방법을 선택 사용한다. 상기 반응으로 제조된 티오메틸페놀 유도체에, 일정량의 산을 첨가하면, 유기층에 잔존하는 아미노메탄올이 분해하거나 물층으로 제거하여 무색의 티오메틸페놀 유도체가 생성된다.Generally, when aminomethanol, an intermediate produced in the reaction, remains in the organic layer, the aminomethanol is oxidized over time to cause discoloration of the thiomethylphenol derivative. The present invention uses a method using an acid as a purification method that is particularly effective in discoloration. When a certain amount of acid is added to the thiomethylphenol derivative prepared by the above reaction, aminomethanol remaining in the organic layer is decomposed or removed with a water layer to produce a colorless thiomethylphenol derivative.
상기 정제에 사용되는 산은 상기에서 언급한 반응에 사용되는 산의 종류와 동일하다. 상기 정제에 사용되는 산은 염기 1 당량에 대하여 1 ∼ 50 당량 범위, 바람직하기로는 3 ∼ 10 당량 범위로 사용하는 바, 사용량이 1 당량 미만이면 변색 가능성이 있으나 50 당량을 초과하는 경우에도 변색이 발생하지 않는다. 첨가하는 산은 용매에 용해하여 사용하거나, 용매없이 사용 가능하며, 만일 용매를 사용하는 경우에는 반응에서 사용된 용매와 동일한 것을 사용할 수 있다. 이때, 용매는 정제에 사용되는 산 1 당량에 대하여 0.1 ∼ 10 당량 범위로 사용하는 것이 좋다.The acid used for the purification is the same as the type of acid used for the reaction mentioned above. The acid used in the purification is used in the range of 1 to 50 equivalents, preferably 3 to 10 equivalents, based on 1 equivalent of base. If the amount is less than 1 equivalent, discoloration may occur, but discoloration may occur even when it exceeds 50 equivalents. I never do that. The acid to be added may be dissolved in a solvent or used without a solvent. If a solvent is used, the same acid as that used in the reaction may be used. At this time, the solvent is preferably used in the range of 0.1 to 10 equivalents relative to 1 equivalent of the acid used for purification.
상기 정제과정으로 얻어진 티오메틸페놀 유도체의 황색지수(YI)는 1 ∼ 15 범위, 바람직하기로는 1 ∼ 8 범위를 유지한다.The yellow index (YI) of the thiomethylphenol derivative obtained by the above purification process is maintained in the range of 1 to 15, preferably 1 to 8.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
실시예 1 : 2,4-비스(n-옥틸티오메틸)-6-메틸페놀의 제조Example 1 Preparation of 2,4-bis (n-octylthiomethyl) -6-methylphenol
o-크레졸 (6.8 g), 파라포름알데히드 (4 g), n-옥탄티올 (18.5 g), 디메틸아민 (0.2 당량) 혼합액, 용매로 물 (5 당량)에 아세트산 (0.15 당량)을 첨가한 후, 120 ℃에서 2 시간 반응시켜 반응생성물을 얻었다. 반응생성물로부터 분리된 유기층을 감압농축하여 농축된 액체의 티오메틸페놀 유도체를 얻었다. o-cresol (6.8 g), paraformaldehyde (4 g), n-octanethiol (18.5 g), dimethylamine (0.2 equiv) mixture, acetic acid (0.15 equiv) to water (5 equiv) as solvent The mixture was reacted at 120 ° C. for 2 hours to obtain a reaction product. The organic layer separated from the reaction product was concentrated under reduced pressure to obtain a concentrated thiomethylphenol derivative.
상기에서 얻어진 티오메틸페놀 유도체의 전환율은 100 %이고, 순도는 97 %이었다.The conversion rate of the thiomethylphenol derivative obtained above was 100%, and the purity was 97%.
실시예 2 ∼ 4 : 2,4-비스(n-옥틸티오메틸)-6-메틸페놀의 제조Examples 2-4: Preparation of 2,4-bis (n-octylthiomethyl) -6-methylphenol
상기 실시예 1과 동일하게 실시하되, 다음 표 1에 나타낸 바와 같이 염기의 종류, 산의 종류 및 반응조건을 달리하여 액체의 티오메틸페놀 유도체를 얻었다. In the same manner as in Example 1, but as shown in the following Table 1, the thiomethylphenol derivative was obtained by varying the type of base, type of acid, and reaction conditions.
비교예 1 ∼ 6 : 2,4-비스(n-옥틸티오메틸)-6-메틸페놀의 제조Comparative Examples 1-6: Preparation of 2,4-bis (n-octylthiomethyl) -6-methylphenol
상기 실시예 1과 동일하게 실시하되, 산의 사용을 배제하고, 다음 표 2에 나타낸 바와 같이 용매종류, 염기의 종류, 반응조건을 달리하여 액체의 티오메틸페놀 유도체를 얻었다. The same procedure as in Example 1 was carried out except for the use of an acid, and as shown in Table 2 below, the solvent type, the type of base, and the reaction conditions were changed to obtain a liquid thiomethylphenol derivative.
상기 표 1과 표 2에서 살펴본 바와 같이, 본 발명에 따라 염기, 산 및 용매를 동시에 사용한 실시예 1 ∼ 3이 비교예 1 ∼ 6에 비해 반응조건이 보다 온화하다는 것을 확인할 수 있었다.As described in Table 1 and Table 2, according to the present invention it was confirmed that Examples 1 to 3 using a base, an acid, and a solvent at the same time, the reaction conditions are more gentle than Comparative Examples 1 to 6.
구체적으로, 종래에 공지된 직쇄형 아민인 디메틸아민, 디프로필아민 및 디부틸아민 등만을 사용한 비교예 1 ∼ 3의 경우 반응이 진행되지 않았거나 약간 낮은 전환율이 보였다. 또한, 직쇄형 아민인 디메틸아민, 디프로필아민 및 벤질메틸아민 등과 용매를 동시에 사용한 비교예 4 ∼ 6의 경우에도 반응이 진행되지 않았거나 약간 낮은 전환율이 보였다. Specifically, in Comparative Examples 1 to 3 using only conventionally known linear amines such as dimethylamine, dipropylamine, dibutylamine, etc., the reaction did not proceed or a slightly lower conversion rate was observed. In addition, in the case of Comparative Examples 4 to 6, in which dimethylamine, dipropylamine, benzylmethylamine, and the like, which were linear amines, were used at the same time, the reaction did not proceed or a slightly lower conversion rate was observed.
그러나, 디메틸아민, 디프로필아민 및 벤질메틸아민 등의 직쇄형 아민에 용매와 산을 사용한 실시예 1 ∼ 4의 경우 보다 온화한 반응조건에서 전환율 및 순도가 높은 결과를 얻었다.However, in Examples 1 to 4 in which a solvent and an acid were used for linear amines such as dimethylamine, dipropylamine and benzylmethylamine, higher conversion and purity were obtained under milder reaction conditions.
결론적으로, 직쇄형 아민, 산 및 반응용매가 동시에 사용된 조건하에서 반응이 수행되는 경우 본 발명에서 목적으로 하는 온화한 반응조건하에서 수행된다는 것을 확인할 수 있었다.In conclusion, it was confirmed that when the reaction is performed under the conditions in which the linear amine, the acid and the reaction solvent are used at the same time, the reaction is performed under the mild reaction conditions of the present invention.
실시예 5 : 2,6-비스(n-옥틸티오메틸)-4-tert-부틸페놀의 제조Example 5 Preparation of 2,6-bis (n-octylthiomethyl) -4-tert-butylphenol
4-tert-부틸페놀 (9.5 g), 파라포름알데히드 (4 g), n-옥탄티올 (18.5 g), 디메틸아민 (0.2 당량) 혼합액, 용매로 물 (5 당량)에 아세트산 (0.15 당량)을 첨가한 후, 120 ℃에서 2 시간 반응시켜 반응생성물을 얻었다. 반응생성물로부터 분리된 유기층을 감압농축하여 무색 액체의 티오메틸페놀 유도체를 얻었다. 상기에서 제조된 티오메틸페놀 유도체는 전환율이 98%이고, 순도는 97%를 나타내었다. 4-tert-butylphenol (9.5 g), paraformaldehyde (4 g), n-octanethiol (18.5 g), dimethylamine (0.2 equiv) mixture, acetic acid (0.15 equiv) in water (5 equiv) with solvent After the addition, the mixture was reacted at 120 ° C. for 2 hours to obtain a reaction product. The organic layer separated from the reaction product was concentrated under reduced pressure to obtain a thiomethylphenol derivative as a colorless liquid. The thiomethylphenol derivative prepared above had a conversion of 98% and a purity of 97%.
실시예 6 : 2,2-비스[4,4'-디히드록시-3,3'5,5'-테트라키스(n-옥틸티오메틸)페놀]프로판의 제조Example 6 Preparation of 2,2-bis [4,4'-dihydroxy-3,3'5,5'-tetrakis (n-octylthiomethyl) phenol] propane
비스페놀 (7.2 g), 파라포름알데히드 (4 g), n-옥탄티올 (18.5 g), 디메틸아민 (0.2 당량) 혼합액, 용매로 물 (5 당량)에 아세트산 (0.15 당량)을 첨가한 후, 120 ℃에서 2 시간 반응시켜 반응생성물을 얻었다. 반응생성물로부터 분리된 유기층을 감압농축하여 무색 액체의 티오메틸페놀 유도체를 얻었다. 상기에서 제조된 티오메틸페놀 유도체는 전환율이 97 %이고, 순도는 93%를 나타내었다. Bisphenol (7.2 g), paraformaldehyde (4 g), n-octanethiol (18.5 g), dimethylamine (0.2 equiv) mixture, acetic acid (0.15 equiv) in water (5 equiv) as solvent, 120 The reaction product was obtained by reacting at 2 ° C. for 2 hours. The organic layer separated from the reaction product was concentrated under reduced pressure to obtain a thiomethylphenol derivative as a colorless liquid. The thiomethylphenol derivative prepared above had a conversion of 97% and a purity of 93%.
실시예 7 : 2,4-비스(n-옥틸티오메틸)-6-벤질페놀의 제조Example 7 Preparation of 2,4-bis (n-octylthiomethyl) -6-benzylphenol
2-벤질페놀 (11.6 g), 파라포름알데히드 (4 g), n-옥탄티올 (18.5 g), 디메틸아민 (0.2 당량) 혼합액, 용매로 물 (5 당량)에 아세트산 (0.15 당량)을 첨가한 후, 120 ℃에서 2 시간 반응시켜 반응생성물을 얻었다. 반응생성물로부터 분리된 유기층을 감압농축하여 무색 액체의 티오메틸페놀 유도체를 얻었다. 상기에서 제조된 티오메틸페놀 유도체는 전환율이 94 %이고, 순도는 92%를 나타내었다. 2-benzylphenol (11.6 g), paraformaldehyde (4 g), n-octanethiol (18.5 g), dimethylamine (0.2 equiv) mixture, acetic acid (0.15 equiv) in water (5 equiv) as solvent Thereafter, the mixture was reacted at 120 ° C. for 2 hours to obtain a reaction product. The organic layer separated from the reaction product was concentrated under reduced pressure to obtain a thiomethylphenol derivative as a colorless liquid. The thiomethylphenol derivative prepared above had a conversion of 94% and a purity of 92%.
실시예 8 ∼ 10 : 2,4-비스(n-옥틸티오메틸)-6-메틸페놀의 정제방법Examples 8 to 10: Purification of 2,4-bis (n-octylthiomethyl) -6-methylphenol
상기 실시예 1 얻어진 반응생성물로부터 분리된 유기층을 산 세척한 후 1시간동안 감압하여 농축된 무색 액체의 티오메틸페놀 유도체를 얻었다. 이때, 농축된 생성물 원액의 투과도는 UV-vis 스펙트로메타의 425 nm에서 측정하였고, 변색은 농축된 생성물 원액의 황색지수(yellowness index: YI)을 측정함으로써 결정하였다.The organic layer separated from the reaction product obtained in Example 1 was washed with acid and decompressed for 1 hour to obtain a concentrated thiomethylphenol derivative as a colorless liquid. At this time, the permeability of the concentrated product stock was measured at 425 nm of UV-vis spectrometer, and the color change was determined by measuring the yellowness index (YI) of the concentrated product stock.
비교예 7: 2,4-비스(n-옥틸티오메틸)-6-메틸페놀의 정제방법Comparative Example 7: Purification of 2,4-bis (n-octylthiomethyl) -6-methylphenol
상기 실시예 2과 동일하게 실시하여 얻어진 반응생성물로부터 분리된 유기층을 산 세척 없이 감압 농축하여 노란색 액체의 티오메틸페놀 유도체를 얻었다. The organic layer separated from the reaction product obtained in the same manner as in Example 2 was concentrated under reduced pressure without acid washing to obtain a thiomethylphenol derivative as a yellow liquid.
상기 표 3에서 나타낸 바와 같이 실시예 8 ∼ 10은 산 처리한 후 감압농축한 결과 무색 액체의 반응생성물을 얻은 반면에 비교예 7는 정제과정을 수행하지 않고 감압 농축한 결과 연노란색 액체의 반응생성물을 얻었다. 정제과정을 수행하지 않은 경우에는 색을 나타내므로 투과도가 현저히 낮으며 황색지수 범위로 높다는 것을 확인할 수 있었다. As shown in Table 3, Examples 8 to 10 obtained a reaction product of a colorless liquid as a result of concentration under reduced pressure after treatment with acid, whereas Comparative Example 7 was a reaction product of a light yellow liquid as a result of concentration under reduced pressure without performing a purification process. Got. When the purification process was not performed, the color was remarkably low and the transmittance was remarkably low and high in the yellow index range.
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| CN103408475A (en) * | 2013-08-23 | 2013-11-27 | 天津利安隆新材料股份有限公司 | Preparation method of liquid antioxidant 4,6-di(octylsulfanylmethyl) o-cresol |
| CN104761478A (en) * | 2014-06-27 | 2015-07-08 | 江苏佳华新材料科技有限公司 | Preparation method of antioxidant 2,4-(dioctanethiol-6-methyl) phenol |
| CN113045462A (en) * | 2021-03-24 | 2021-06-29 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1520 |
| CN115151528A (en) * | 2020-10-30 | 2022-10-04 | 锦湖石油化学株式会社 | Process for preparing thiomethylphenol derivatives |
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| DE60011569T2 (en) | 2000-04-12 | 2005-08-18 | Kumho Monsanto, Inc. | New antioxidant and process for its preparation |
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| CN103408475A (en) * | 2013-08-23 | 2013-11-27 | 天津利安隆新材料股份有限公司 | Preparation method of liquid antioxidant 4,6-di(octylsulfanylmethyl) o-cresol |
| CN103408475B (en) * | 2013-08-23 | 2015-09-09 | 天津利安隆新材料股份有限公司 | The preparation method of liquid antioxidant 4,6-bis-(pungent thiomethyl) ortho-cresol |
| CN104761478A (en) * | 2014-06-27 | 2015-07-08 | 江苏佳华新材料科技有限公司 | Preparation method of antioxidant 2,4-(dioctanethiol-6-methyl) phenol |
| CN115151528A (en) * | 2020-10-30 | 2022-10-04 | 锦湖石油化学株式会社 | Process for preparing thiomethylphenol derivatives |
| CN113045462A (en) * | 2021-03-24 | 2021-06-29 | 江苏极易新材料有限公司 | Synthesis method of antioxidant 1520 |
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