KR100915946B1 - Synthetic method of tris-3,5-di-t-butyl-4-hydroxybenzylamine - Google Patents
Synthetic method of tris-3,5-di-t-butyl-4-hydroxybenzylamine Download PDFInfo
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- KR100915946B1 KR100915946B1 KR1020080002528A KR20080002528A KR100915946B1 KR 100915946 B1 KR100915946 B1 KR 100915946B1 KR 1020080002528 A KR1020080002528 A KR 1020080002528A KR 20080002528 A KR20080002528 A KR 20080002528A KR 100915946 B1 KR100915946 B1 KR 100915946B1
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- butyl
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- hydroxybenzyl
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- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 238000001308 synthesis method Methods 0.000 claims abstract description 21
- BOQNWBDBDUWBMT-UHFFFAOYSA-N 4-[[bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]amino]methyl]-2,6-ditert-butylphenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BOQNWBDBDUWBMT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 11
- 239000002244 precipitate Substances 0.000 claims abstract description 8
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical group CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 36
- TXBWKXFDLINCMJ-UHFFFAOYSA-N 2,6-ditert-butyl-4-(chloromethyl)phenol Chemical compound CC(C)(C)C1=CC(CCl)=CC(C(C)(C)C)=C1O TXBWKXFDLINCMJ-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 23
- 239000003963 antioxidant agent Substances 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 230000035484 reaction time Effects 0.000 abstract description 11
- 230000003078 antioxidant effect Effects 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 239000000376 reactant Substances 0.000 abstract description 5
- 235000013305 food Nutrition 0.000 abstract description 4
- 239000003921 oil Substances 0.000 abstract description 4
- 238000004904 shortening Methods 0.000 abstract description 3
- 231100000419 toxicity Toxicity 0.000 abstract description 3
- 230000001988 toxicity Effects 0.000 abstract description 3
- 230000002159 abnormal effect Effects 0.000 abstract description 2
- 239000007983 Tris buffer Substances 0.000 abstract 1
- 150000001412 amines Chemical class 0.000 abstract 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 150000001875 compounds Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- JJQCWPWUHZFKBN-UHFFFAOYSA-N 2,6-ditert-butyl-4-methylidenecyclohexa-2,5-dien-1-one Chemical compound CC(C)(C)C1=CC(=C)C=C(C(C)(C)C)C1=O JJQCWPWUHZFKBN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 t -butyl Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/46—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C215/48—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups
- C07C215/52—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by hydroxy groups linked by carbon chains having two carbon atoms between the amino groups and the six-membered aromatic ring or the condensed ring system containing that ring
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2200/00—Function of food ingredients
- A23V2200/02—Antioxidant
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 플라스틱, 식품, 오일 등에 광범위하게 이용되는 산화방지제인 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 합성방법에 관한 것으로, 3,5-디-t-부틸-4-히드록시벤질클로라이드를 비극성 용매에 용해한 후 극성 용매를 적가하는 단계 및 얻어진 침전물을 탈색하는 단계를 포함하는 것이다.The present invention relates to a method for synthesizing tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine, an antioxidant widely used in plastics, foods, oils, and the like. Dissolving -butyl-4-hydroxybenzylchloride in a nonpolar solvent followed by dropwise addition of the polar solvent and decolorizing the precipitate obtained.
상기 본 발명의 합성방법은 비극성 용매와 극성 용매의 이상반응을 이용하여 합성하는 것으로, 기존 합성방법에 대비하여 취급이 용이하고 유독성이 줄어든 용매를 사용하여 합성 공정 중 발생할 수 있는 유해성을 낮출 수 있으며, 반응물을 저온 상태로 만들기 위해 소모되는 에너지를 최소화 시킬 수 있을 뿐만 아니라 반응시간을 단축하고 높은 수율을 얻음으로써 경제성이 뛰어난 것이다.The synthesis method of the present invention is synthesized by using an abnormal reaction of a non-polar solvent and a polar solvent, it is possible to lower the hazards that may occur during the synthesis process using a solvent that is easy to handle and reduced toxicity compared to the existing synthesis method. In addition, it is economical by not only minimizing the energy consumed to bring the reactants to a low temperature, but also shortening the reaction time and obtaining a high yield.
트리스, 아민, 합성방법, 산화방지제, 용매, 경제성 Tris, Amine, Synthetic Method, Antioxidant
Description
본 발명은 플라스틱, 식품, 오일 등에 광범위하게 이용되는 산화방지제인 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민{Tris-(3,5-di-t-butyl-4-hydroxybenzyl)amine}의 합성방법에 관한 것으로, 3,5-디-t-부틸-4-히드록시벤질클로라이드를 비극성 용매에 용해한 후 극성 용매를 적가하는 단계 및 얻어진 침전물을 탈색하는 단계를 포함하는 것이다.The present invention provides tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine, an antioxidant widely used in plastics, foods, oils, and the like.Tris- (3,5-di- t- butyl- 4-hydroxybenzyl) amine}, comprising dissolving 3,5-di-t-butyl-4-hydroxybenzylchloride in a non-polar solvent and dropping the polar solvent and decolorizing the precipitate obtained. It is.
상기 본 발명의 합성방법은 비극성 용매와 극성 용매의 이상반응을 이용하여 합성하는 것으로, 기존 합성방법에 대비하여 취급이 용이하고 유독성이 줄어든 용매를 사용하여 합성 공정 중 발생할 수 있는 유해성을 낮출 수 있으며, 반응물을 저온 상태로 만들기 위해 소모되는 에너지를 최소화 시킬 수 있을 뿐만 아니라 반응시간을 단축하고 높은 수율을 얻음으로써 경제성이 뛰어난 것이다.The synthesis method of the present invention is synthesized by using an abnormal reaction of a non-polar solvent and a polar solvent, it is possible to lower the hazards that may occur during the synthesis process using a solvent that is easy to handle and reduced toxicity compared to the existing synthesis method. In addition, it is economical by not only minimizing the energy consumed to bring the reactants to a low temperature, but also shortening the reaction time and obtaining a high yield.
산화방지제(antioxidants)는 활성산소의 주요인인 프리라디칼(free radical)이 가지는 에너지를 줄여주거나 프리라디칼의 생성을 중지시켜 활성 산소의 작용을 멈추게 한다. Antioxidants reduce the energy of free radicals, which are the mains of free radicals, or stop the action of free radicals by stopping the production of free radicals.
또한 프리라디칼의 저해 작용을 최소화시키기 위하여 산화적 연쇄반응을 방해하여 안정한 상태의 분자 구조를 유지하게 한다. In addition, in order to minimize the inhibitory action of free radicals, the oxidative chain reaction is interrupted to maintain a stable molecular structure.
산화방지제는 반응성이 좋은 수소원자를 제공하여 프리라디칼을 차단하거나 안정화 시키며, 용도와 화합물 별로 여러 종류가 있으나, 플라스틱, 식품, 오일 등에 가장 포괄적으로 사용되는 것으로 페놀 계열의 산화방지제가 있다. Antioxidant blocks or stabilizes free radicals by providing highly reactive hydrogen atoms, but there are many kinds according to uses and compounds, but most widely used in plastics, foods, oils, etc., there are phenolic antioxidants.
보통, 산화방지제는 더 이상 산화가 진행되지 않도록 안정한 낮은 에너지 프리라디칼을 형성해야 한다. 이런 면에서 페놀계 화합물은 안정한 공명 혼성체(resonance hybrid)를 형성하므로 가장 적합한 화학적 구조를 가진 화합물에 해당 된다. 또한 페놀 자체에는 산화방지제로서의 활성을 갖지는 않으나 2, 4, 6번 위치에 알킬기가 치환되면 매우 강한 산화방지제로 전환 된다. 그 이유는 알킬기의 electron donating 성질 때문에 페녹시 프리라디칼이 더욱 더 안정화되기 때문이다. 그러므로 알킬기가 총 6개가 치환된 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민은 강력한 산화방지제 화합물이라고 할 수 있다. Usually, antioxidants should form stable low energy free radicals so that no further oxidation proceeds. In this respect, the phenolic compound is a compound having the most suitable chemical structure because it forms a stable resonance hybrid. In addition, phenol itself does not have an activity as an antioxidant, but when an alkyl group is substituted at positions 2, 4 and 6, it is converted into a very strong antioxidant. This is because phenoxy free radicals are more stabilized due to the electron donating nature of alkyl groups. Therefore, tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine having a total of 6 alkyl groups substituted is a powerful antioxidant compound.
[반응식 1] 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 초기 합성 방법(Acta Chemica Scandinavica, 20(8). 2211-2214.)Scheme 1 Initial synthesis of tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine (Acta Chemica Scandinavica, 20 (8). 2211-2214.)
기존 의 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 합성법은 2단계를 거쳐야 했다. The existing method of synthesizing tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine had to go through two steps.
첫 번째 단계는 2,6-디-t-부틸-4-메틸페놀을 니트로소디술포네이트로 산화반응시켜 2,6-디-t-부틸-4-메틸렌시클로헥사-2,5-디엔온을 합성하였다. 반응시간은 2 일이 소요된다. The first step is the oxidation of 2,6-di- t -butyl-4-methylphenol with nitrosodisulfonate to give 2,6-di- t -butyl-4-methylenecyclohexa-2,5-dienone. Synthesized. The reaction time takes 2 days.
두 번째 단계는 2,6-디-t-부틸-4-메틸렌시클로헥사-2,5-디엔온에 농축된 암모니아를 가하여 4시간 교반 후 침전이 생성되도록 2 일 동안 방치 하였다. 최종적으로, 흰색의 고체 화합물인, 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민이 얻어 지며, 수율은 37 %이다. In the second step, concentrated ammonia was added to 2,6-di- t -butyl-4-methylenecyclohexa-2,5-dienone, followed by stirring for 4 hours, and left for 2 days to form a precipitate. Finally, a white solid compound, tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine, is obtained and the yield is 37%.
상기 반응 조건은 2단계를 거쳐야 하고, 반응시간이 너무 길고, 또한 생성물의 수율 또한 낮았다. The reaction conditions had to go through two stages, the reaction time was too long, and the yield of the product was also low.
이러한 합성법을 개선하고자 다음과 같은 합성법이 개발되었다. To improve this synthesis method, the following synthesis method was developed.
[반응식 2] 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 기존 합성 방법(WO 97/31004)Scheme 2 Conventional synthesis method of tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine (WO 97/31004)
상기 WO 97/31004의 12페이지에 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 합성법이 발표되었다. A method for synthesizing tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine is disclosed on page 12 of WO 97/31004.
WO 97/31004의 합성법은 기존의 2단계 합성법을 1단계로 줄이고 반응시간을 1 일로 대폭 줄인 합성법으로 자세한 내용은 다음과 같다. The synthesis method of WO 97/31004 is a synthesis method in which the conventional two-step synthesis method is reduced to one step and the reaction time is greatly reduced to one day.
3,5-디-t-부틸-4-히드록시벤질클로라이드(6.7g, 0.026 mole)를 디클로로메 탄(50mL)에 녹인 후 -15 ~ -20 oC에서 암모니아 가스가 녹아들어가 있는 디클로로메탄(200mL)에 천천히 적가 한다. 혼합물을 실온에서 하루 동안 교반시킨 후, 반응물을 여과하고, 물 100mL 씩 세 번에 걸쳐서 세척한다. 세척된 반응물을 무수 황산마그네슘 하에서 건조 한다. 반응물의 수분을 제거 한 후, n-헵탄으로 재결정하여 노란색의 고체 화합물을 얻을 수 있다, 최종적으로 4.2 g의 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민을 얻을 수 있으며, 최종 수율은 37 %이다. 3,5-di-t-butyl-4-hydroxybenzylchloride (6.7 g, 0.026 mole) was dissolved in dichloromethane (50 mL) and dichloromethane with ammonia gas dissolved at -15 to -20 o C ( 200 mL) slowly. After the mixture is stirred at room temperature for one day, the reaction is filtered and washed three times with 100 mL of water. The washed reaction is dried under anhydrous magnesium sulfate. After removing the water of the reaction, it is recrystallized with n-heptane to obtain a yellow solid compound, finally 4.2 g of tris- (3,5-di- t -butyl-4-hydroxybenzyl) amine And the final yield is 37%.
상기 합성법은 초기 합성법에 비교하여, 반응시간 및 합성단계는 줄어들었지만 수율은 같았으며, 최종 생성물의 색상이 노란색이었다. Compared to the initial synthesis method, the synthesis method reduced the reaction time and the synthesis step, but the yield was the same, and the final product was yellow in color.
트리스-(3,5-디-t-부틸-4-히드록시벤질)아민은 매우 강력한 페놀계 산화방지제이지만, 일반적으로 합성하기 위한 반응시간이 길 뿐만 아니라, 수율 또한 낮다. 따라서, 많이 사용되어지는 산화방지제는 아니고, 플라스틱 제조 공정 중 일부와 항공기유 등에 첨가제로 사용되어진다. 하지만, 보다 간단하고 경제적인 합성방법을 개발하게 되면 강력한 산화방지제로서의 매력에 의하여 보다 많은 사용이 이루어질 것이다.Tris- (3,5-di- t -butyl-4-hydroxybenzyl) amine is a very powerful phenolic antioxidant, but generally has a long reaction time for synthesis and a low yield. Therefore, it is not a widely used antioxidant, and is used as an additive in part of plastic manufacturing process, aircraft oil, and the like. However, the development of simpler and more economical synthetic methods will make more use due to its appeal as a powerful antioxidant.
출발물질인 3,5-디-t-부틸-4-히드록시벤질클로라이드는 공기 중에서 극성이 높은 용매를 만나면 쉽게 벤질클로라이드의 클로라이드가 분해되어 버린다. 그러므로 3,5-디-t-부틸-4-히드록시벤질클로라이드를 비극성 용매에 녹여서 보관하게 된다. WO 97/31004에서의 합성법에는 3,5-디-t-부틸-4-히드록시벤질클로라이드를 디클로로메탄에 녹여서 보관 및 출발 물질의 용매로 사용하였다. The starting material 3,5-di-t-butyl-4-hydroxybenzyl chloride easily decomposes the chloride of benzyl chloride when it encounters a highly polar solvent in the air. Therefore, 3,5-di-t-butyl-4-hydroxybenzylchloride is stored in a nonpolar solvent. In the synthesis in WO 97/31004, 3,5-di-t-butyl-4-hydroxybenzylchloride was dissolved in dichloromethane and used as a solvent for storage and starting material.
보통 산화방지제는 다양한 제품의 첨가제로 사용되고, 플라스틱에서의 황변현상을 방지하고, 식품에서는 변색 및 상함을 방지하기 때문에 보통 흰색의 색상을 띈다. 초기 합성법으로 제조된 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민은 흰색의 고체였으나, 반응시간 및 합성 단계가 단축된 합성법에서는 노란색의 고체 였다. 최종 화합물이 노란색을 띄는 이유는 최종 생성물에 미반응된 출발 물질이 남아있기 때문일 확률이 매우 높은데 보통 벤질클로라이드의 클로라이드 분해 시 진한 노란색을 띄기 때문이다. 이러한 문제점은 1차적으로, 반응의 완결화 및 2차적으로, 미량의 미반응물 발생 시 세척하여 완전 제거 하는 방법을 이용하여야 할 것이다. Antioxidants are usually used as additives in various products, and are usually white in color because they prevent yellowing in plastics and prevent discoloration and spoilage in foods. Tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine prepared by the initial synthesis was a white solid, but a yellow solid in the synthesis method with shorter reaction time and synthesis step. The final compound is yellowish because the unreacted starting material remains in the final product, which is usually dark yellow when the chloride breakdown of benzylchloride. This problem should be primarily used to complete the reaction and secondly, to remove and completely remove the traces of unreacted material.
따라서, 본 발명에서는 이러한 점을 감안하여 연구 개발된 것으로, 기존 합성방법에 대비하여 취급이 용이하고 유독성이 줄어든 용매를 사용하여 합성 공정 중 발생할 수 있는 유해성을 낮출 수 있으며, 반응물을 저온 상태로 만들기 위해 소모되는 에너지를 최소화 시킬 수 있을 뿐만 아니라 반응시간을 단축하고 높은 수율을 얻음으로써 경제성이 뛰어난 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 합성방법을 제공하고자 한다.Therefore, the present invention has been researched and developed in view of this point, it is possible to lower the hazards that may occur during the synthesis process by using a solvent that is easy to handle and reduced toxicity compared to the existing synthetic method, making the reactant to a low temperature state To provide a method for synthesizing tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine that is economical by minimizing the energy consumed for the purpose and shortening the reaction time and obtaining high yield. do.
본 발명은 비극성 용매와 극성 용매의 이상반응을 이용하여 합성하는 것으로, 3,5-디-t-부틸-4-히드록시벤질클로라이드를 비극성 용매에 용해한 후 극성 용매를 적가하는 단계 및 얻어진 침전물을 탈색하는 단계를 포함하는 것이 특징이다.The present invention is synthesized by using an ideal reaction between a nonpolar solvent and a polar solvent, and dissolving 3,5-di-t-butyl-4-hydroxybenzyl chloride in a nonpolar solvent, dropping the polar solvent dropwise and the obtained precipitate It is characterized by including the step of bleaching.
본 발명에 따르면 기존 합성방법 대비하여, 유독성이 큰 디클로로메탄 대신 n-헵탄을 사용하고, 다루기 힘들고, 유독성이 큰 암모니아 가스 대신 암모니아수를 사용하여 합성 공정 중 발생할 수 있는 유해성을 낮출 수 있을 뿐만 아니라, 반응물 첨가 온도를 -15 ∼ -20 oC에서 5 oC로 올려 실제 공정에서 저온 상태로 만들기 위해 소모되는 에너지를 최소화 시킬 수 있으며, 또한 하루가 소요되는 반응시간을 최대 4시간으로 단축하였을 뿐만 아니라, 최종적으로 92%의 높은 수율을 얻어, 전체적으로 경제성이 뛰어난 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민 합성법이다. According to the present invention, in addition to the conventional synthesis method, using n-heptane instead of toxic dichloromethane, and ammonia water instead of unwieldy, toxic ammonia gas can reduce the hazards that may occur during the synthesis process, By increasing the temperature of the reactant addition from -15 to -20 o C to 5 o C, it is possible to minimize the energy consumed to bring it to a low temperature in the actual process, and also to reduce the reaction time taken up to 4 hours. Finally, it is a method of synthesizing tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine, which finally has a high yield of 92% and is excellent in overall economic efficiency.
본 발명은 3,5-디-t-부틸-4-히드록시벤질클로라이드를 비극성 용매에 용해한 후 극성 용매를 적가하는 단계 및 얻어진 침전물을 탈색하는 단계를 포함한다.The present invention comprises the steps of dissolving 3,5-di-t-butyl-4-hydroxybenzylchloride in a nonpolar solvent followed by dropwise addition of the polar solvent and decolorizing the precipitate obtained.
여기서, 상기 비극성 용매는 n-헵탄이고 극성 용매는 암모니아수인 것이 바람직하다.Here, it is preferable that the nonpolar solvent is n-heptane and the polar solvent is ammonia water.
본 발명에서의 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 새로운 합성법은 하기 반응식 3과 같다. The new synthesis of tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine in the present invention is shown in Scheme 3 below.
[반응식 3]Scheme 3
기존의 합성법에는 3,5-디-t-부틸-4-히드록시벤질클로라이드를 디클로로메탄 에 녹여서 보관 및 출발 물질의 용매로 사용하였으나 본 발명에서는 n-헵탄을 보관 및 출발 물질의 용매로 사용하였다. In the conventional synthesis method, 3,5-di-t-butyl-4-hydroxybenzyl chloride was dissolved in dichloromethane and used as a solvent for storage and starting materials. In the present invention, n-heptane was used as a solvent for storage and starting materials. .
그 이유는 디클로로메탄의 유전상수는 9.1이고, n-헵탄의 유전상수는 1.9이다. 즉 n-헵탄이 디클로로메탄에 비하여 상대적으로 훨씬 비극성이다. 그러므로 n-헵탄을 용매로 사용 시 클로라이드의 분해를 상대적으로 최소화 시킬 수 있었다. The reason is that the dielectric constant of dichloromethane is 9.1 and the dielectric constant of n-heptane is 1.9. That is, n-heptane is relatively much more nonpolar than dichloromethane. Therefore, the decomposition of chloride was relatively minimized when using n-heptane as a solvent.
기존 합성법은 SN2 반응을 기본으로 하지만, 본 발명에서는 SN1 반응이 일어남을 전제로 한다. 보통 SN2 반응은 용매화에 의해 공격하는 친핵체의 바닥상태 에너지 준위가 낮아지므로, 극성용매에 의해서 반응속도가 감소한다. 그러나 SN1 반응은 용매화에 의해 카르보 양이온으로 되는 전이상태의 에너지 준위가 낮아지므로 극성용매에 의해 반응속도가 증가한다. Conventional synthesis methods are based on the S N 2 reaction, but in the present invention it is assumed that the S N 1 reaction occurs. In general, the reaction of S N 2 lowers the ground state energy level of the nucleophile attacked by solvation, so that the reaction rate decreases due to the polar solvent. However, in the S N 1 reaction, the reaction rate is increased by the polar solvent because the energy level of the transition state to the carbo cation is lowered by solvation.
즉, 기존의 암모니아 가스를 투입 시 SN2 반응 에만 의존하였던 것을 암모니아수를 가하여 SN1 반응이 일어나게 하였다. 암모니아수에 포함되어 있는 물은 극성용매로서, 3,5-디-t-부틸-4-히드록시벤질클로라이드에 있는 클로라이드기의 자발적인 해리를 통하여, 매우 안정한 벤질 카르보 양이온을 형성하게 되어, 매우 빠른 반응이 진행하게 된다. 특히 SN1 반응에서 n-헵탄과 같은 탄화수소 용매에서 물로 용매 변화를 했을 때의 반응 속도 증가는 매우 커서 정확히 측정하기 어렵다. 그러나, 위의 반응을 잘 진행시키기 위해서는 매우 격렬한 교반을 필요로 한다. 그 이유로 n-헵탄은 소수성이고, 물은 친수성이기 때문에 서로 전혀 섞이지 않기 때문이 다. 따라서, 본 발명에서는 2상(two phase) 반응을 위한 격렬한 교반을 통해 높은 수율의 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민을 얻을 수 있는 것이다.In other words, the addition of ammonia water caused the S N 1 reaction to depend on the S N 2 reaction when the existing ammonia gas was added. The water contained in the ammonia water is a polar solvent, and spontaneous dissociation of the chloride group in 3,5-di-t-butyl-4-hydroxybenzyl chloride forms a very stable benzyl carbo cation, which is very fast. The reaction proceeds. In particular, the increase in the reaction rate when the solvent is changed to water in a hydrocarbon solvent such as n-heptane in the S N 1 reaction is very large and difficult to accurately measure. However, very vigorous agitation is required for the reaction to proceed well. This is because n-heptane is hydrophobic and water is hydrophilic and does not mix with each other at all. Accordingly, in the present invention, high yield of tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine can be obtained through vigorous stirring for two phase reaction.
이하, 실시예를 통하여 좀더 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
실시예 1 Example 1
반응기에 3,5-디-t-부틸-4-히드록시벤질클로라이드(5.1g, 0.02 mole)를 n-헵탄 (100mL)에 녹인 후 5 oC에서 28 % 암모니아수 200 mL를 천천히 적가 한다. 실온에서 4시간 동안 반응물을 교반 하면, 주황색의 침전물이 과량 형성된다. 침전물을 여과한 후, 물 100 mL로 1회 세척 하면, 노란색으로 탈색이 되고, n-헵탄 50 mL로 1회 세척 하게 되면 흰색으로 탈색하게 된다. 최종 생성물을 건조 후 보관한다. 최종적으로 4.13 g의 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민을 얻을 수 있으며, 최종 수율은 92 %이다. Dissolve 3,5-di-t-butyl-4-hydroxybenzylchloride (5.1 g, 0.02 mole) in n-heptane (100 mL) and slowly add dropwise 200 mL of 28% ammonia water at 5 ° C to the reactor. When the reaction is stirred for 4 hours at room temperature, an orange precipitate is formed in excess. The precipitate is filtered off and washed once with 100 mL of water, which is decolorized yellow. Once washed with 50 mL of n-heptane, it is decolorized white. The final product is stored after drying. Finally 4.13 g of tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine can be obtained with a final yield of 92%.
상기 실시예 1의 화합물에 대한 NMR 측정결과 그래프를 도 1에 나타낸다.A graph of NMR measurement results for the compound of Example 1 is shown in FIG. 1.
1H NMR (CDCl3): δ 1.43(s, 54H, t-butyl), 3.42(s, 6H, -CH2), 5.04(s, 3H, -OH), 7.20(s, 6H, ArH). 1 H NMR (CDCl 3 ): δ 1.43 (s, 54H, t -butyl), 3.42 (s, 6H, -CH 2 ), 5.04 (s, 3H, -OH), 7.20 (s, 6H, ArH).
위와 같이, 본 발명의 트리스-(3,5-디-t-부틸-4-히드록시벤질)아민의 합성법 은 WO 97/31004의 합성법과 비교하여 반응물의 첨가 온도를 -15 ~ -20 oC에서 5 oC로 변경함으로 인한 온도제어에 필요한 에너지를 줄일 수 있을 뿐만 아니라, 총 반응 시간을 1 일에서 4시간으로 줄일 수 있었다. 또한 최종 생성물의 색상을 기존 노란색에서 흰색으로 탈색할 수 있었고, 최종적으로 합성 수율을 34 %에서, 92%로 대폭 증가 시킬 수 있을 수 있으므로, 기존 합성법보다 매우 경제적이고, 합리적인 합성법이라고 할 수 있다. As described above, the synthesis method of the tris- (3,5-di-t-butyl-4-hydroxybenzyl) amine of the present invention is compared with the synthesis method of WO 97/31004 and the addition temperature of the reactants is -15 to -20 o C. In addition to reducing the energy required for temperature control by changing from 5 o C to, the total reaction time was reduced from 1 day to 4 hours. In addition, the color of the final product can be discolored from the existing yellow to white, and finally the synthesis yield can be significantly increased from 34% to 92%, it is a very economical and rational synthesis method than the existing synthesis method.
도 1은 본 발명의 실시예 1의 화합물에 대한 NMR 측정결과 그래프1 is a graph of the NMR measurement results for the compound of Example 1 of the present invention
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| FR1362558A (en) * | 1963-04-12 | 1964-06-05 | Cie Francaise Des Prod Chim Sh | New additives with antioxidant properties, their preparation and use |
| SU627123A1 (en) | 1977-05-19 | 1978-10-05 | Предприятие П/Я А-7253 | Method of producing tris-(3,5-di-tret-butyl-4-oxybenzyl)-amine |
| US6048995A (en) | 1996-02-21 | 2000-04-11 | Grinter; Trevor John | Process for the preparation of diphosphonate derivatives |
-
2008
- 2008-01-09 KR KR1020080002528A patent/KR100915946B1/en not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1362558A (en) * | 1963-04-12 | 1964-06-05 | Cie Francaise Des Prod Chim Sh | New additives with antioxidant properties, their preparation and use |
| SU627123A1 (en) | 1977-05-19 | 1978-10-05 | Предприятие П/Я А-7253 | Method of producing tris-(3,5-di-tret-butyl-4-oxybenzyl)-amine |
| US6048995A (en) | 1996-02-21 | 2000-04-11 | Grinter; Trevor John | Process for the preparation of diphosphonate derivatives |
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|---|---|
| KR20090076526A (en) | 2009-07-13 |
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