KR100910880B1 - New synthetic method of aryl iodides from aryl amines via a water-paste form - Google Patents

New synthetic method of aryl iodides from aryl amines via a water-paste form Download PDF

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KR100910880B1
KR100910880B1 KR1020070086825A KR20070086825A KR100910880B1 KR 100910880 B1 KR100910880 B1 KR 100910880B1 KR 1020070086825 A KR1020070086825 A KR 1020070086825A KR 20070086825 A KR20070086825 A KR 20070086825A KR 100910880 B1 KR100910880 B1 KR 100910880B1
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aromatic
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nano
equivalents
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KR20090021919A (en
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지기환
필리모노프 빅터
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울산대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • C07C17/12—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms in the ring of aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/06—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D239/08—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms directly attached in position 2
    • C07D239/10—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C07D239/54—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals
    • C07D239/545—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/553—Two oxygen atoms as doubly bound oxygen atoms or as unsubstituted hydroxy radicals with other hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms with halogen atoms or nitro radicals directly attached to ring carbon atoms, e.g. fluorouracil

Abstract

본 발명은 방향족 아민으로부터 방향족 요오드화물을 합성하는 신규의 방법에 관한 것으로, 유기용매 등을 사용하지 않고 최소량의 물만을 반응물에 첨가하여 물-반죽 상태에서 반응하여 최종생성물을 얻는 것을 특징으로 한다. 반응물로는 방향족 아민, NaNO2(또는 KNO2), p-톨루엔 술폰산(pTsOH), KI(또는 NaI)가 사용된다. The present invention relates to a novel method for synthesizing aromatic iodides from aromatic amines, characterized in that the final product is obtained by reacting in a water-dough state by adding only a minimum amount of water to the reactants without using an organic solvent or the like. The reactants include aromatic amines, NaNO 2 (or KNO 2 ), p -toluene sulfonic acid ( p TsOH), KI (or NaI).

아민, 요오드 Amines, iodine

Description

물-반죽상태에서 방향족 아민으로부터 방향족 요오드화합물을 합성하는 신규의 방법{New synthetic method of aryl iodides from aryl amines via a water-paste form}New synthetic method of aryl iodides from aryl amines via a water-paste form

본 발명은 방향족 아민(aryl amines)으로부터 방향족 요오드화합물(aryl iodides)을 효과적으로 합성하는 새로운 방법에 관한 것이다. 더 상세히는 생체활성 물질 및 전자재료 또는 그 중간체의 합성 시 유용한 물질로 활용되는 방향족 요오드화합물을 방향족 아민화합물로부터 유기 용매를 사용하지 않고 물-반죽(paste) 상태에서 합성하는 방법에 관한 것이다. The present invention relates to a novel method for the effective synthesis of aromatic iodine (aryl iodides) from aromatic amines. More particularly, the present invention relates to a method for synthesizing an aromatic iodine compound, which is used as a useful material for synthesizing a bioactive material and an electronic material or an intermediate thereof, from an aromatic amine compound in a water-paste state without using an organic solvent.

지금까지 알려진 방향족 아민으로부터 방향족 요오드화합물을 합성하는 방법으로는, 소위 Sandmeyer 방법 이외에도 DMSO용매 상에서 HI/KNO2 를 처리한다든가 CH3CN용매 상에서 KI/NaNO2/pTsOH를 처리하는 방법 등이 최근 보고된 바 있다. 그러나 기 개발된 기술은 유기용매를 반응용매로 사용하거나, 다량의 강산을 사용하고, 또는 구리염 등 유해한 반응물을 사용하는 등의 환경적 문제를 야기하는 문제점이 있다.As a method for synthesizing an aromatic iodine compound from the aromatic amines known to date, in addition to the so-called Sandmeyer method, the treatment of HI / KNO 2 in DMSO solvent or the KI / NaNO 2 / p TsOH in CH 3 CN solvent has been recently performed. It has been reported. However, the previously developed technology has a problem of causing an environmental problem such as using an organic solvent as a reaction solvent, using a large amount of strong acid, or using harmful reactants such as copper salts.

본 발명은 방향족 아민화합물로부터 방향족 요오드화합물을 효과적으로 합성하는 기술로서, 상온에서 유기용매와 강한 무기산을 사용하지 않고 물-반죽 상태로 반응물을 일정시간 섞어 높은 수득률로 최종 생성물을 제조하는 매우 간단하고 반응조건이 온화하며 환경친화적인 합성기술이다.The present invention is a technique for effectively synthesizing aromatic iodine compounds from aromatic amine compounds, which is a very simple and reaction in which the final product is produced at a high yield by mixing the reactants in water-dough for a certain time without using an organic solvent and a strong inorganic acid at room temperature. Conditions are gentle and environmentally friendly synthesis technology.

본 발명은 유기용매 등을 사용하지 않고 최소량의 물만을 반응물에 첨가하여 물-반죽 상태에서 방향족 아민과 금속요오드화물을 반응시켜 방향족 요오드화물을 얻는 것을 특징으로 한다. 반응물로는 방향족 아민, NaNO2(또는 KNO2), p-톨루엔 술폰산(pTsOH), KI(또는 NaI)가 사용된다. The present invention is characterized in that an aromatic iodide is obtained by reacting an aromatic amine with a metal iodide in a water-dough state by adding only a minimum amount of water to the reactants without using an organic solvent. The reactants include aromatic amines, NaNO 2 (or KNO 2 ), p -toluene sulfonic acid ( p TsOH), KI (or NaI).

본 발명은 방향족 아민에 pTsOHH2O와 소량의 물을 첨가해 반죽상태를 만든 후 NaNO2(또는 KNO2)를 첨가하고 막대주걱으로 일정시간 섞은 후 KI(또는 NaI)를 첨가하고 일정시간 저어주는 간단한 방법으로 방향족 요오드화합물을 제조할 수 있는 기술이다.In the present invention, p TsOHH 2 O and a small amount of water are added to the aromatic amine to make a dough state, and then NaNO 2 (or KNO 2 ) is added. After mixing for a certain time with a rod spatula, KI (or NaI) can be added and stirred for a certain time to produce an aromatic iodine compound.

본 발명에서는 방향족 아민의 디아조화반응(diazotization)과 중간체인 디아조늄 토실레이트(diazonium tosylate)의 요오드화반응(iodination)이 단계적으로 진행되어야 성공적인 결과가 기대되는 이유로 KI(또는 NaI)는 디아조화반응이 완결 된 후 첨가하여야 좋은 결과를 얻을 수 있다. 본 기술을 사용하면 전자를 주는 기 (실시 예 13-14)는 물론 당기는 기 (실시 예 1-12, 15)로 치환된 방향족 아민화합물로부터 해당 방향족 요오드화합물을 성공적으로 합성할 수 있다. 또한 강산에 예민한 치환기를 갖는 방향족 아민화합물에도 본 발명의 적용이 가능하다. (실시 예 11-13) In the present invention, the diazoization of aromatic amines and the iodination of diazonium tosylate, an intermediate, should be carried out step by step. It should be added after completion to get good results. Using this technique, the aromatic iodine compound can be successfully synthesized from an aromatic amine compound substituted with an electron-giving group (Examples 13-14) as well as a pulling group (Examples 1-12, 15). The present invention can also be applied to aromatic amine compounds having substituents sensitive to strong acids. (Example 11-13)

이하, 본 발명을 실시예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of examples.

실시예 1-16Example 1-16

본 발명에 사용된 반응물과 반응물의 당량비는 방향족 아민(1당량 기준), pTsOHH2O(1-5당량), NaNO2(또는 KNO2, 1-5당량), KI(또는 NaI, 1-5당량)와 소량의 물이다. 실시 예[표 1]의 구체적 합성방법으로는, 상온에서 agate 막대사발에 방향족 아민(2 mmol), pTsOHH2O(6 mmol)과 소량의 물(0.2 ml)을 첨가해 반죽상태를 만든 후 NaNO2(5 mmol)를 첨가하고 막대주걱으로 10-20분 동안 섞은 후 KI(5 mmol)를 첨가하고 10-30분 동안 추가로 저었다. The equivalent ratio of reactants to reactants used in the present invention is aromatic amine (based on 1 equivalent), p TsOHH 2 O (1-5 equivalents), NaNO 2 (or KNO 2 , 1-5 equivalents), KI (or NaI, 1-5 equivalents) ) And a small amount of water. Example [Table 1] As a specific method of synthesis, after the addition of aromatic amine (2 mmol), p TsOHH2O (6 mmol) and a small amount of water (0.2 ml) to agate rod bowl at room temperature to form a dough state NaNO 2 (5 mmol) is added After mixing for 10-20 minutes with a spatula, KI (5 mmol) was added and stirred for an additional 10-30 minutes.

이렇게 얻은 반응생성물에 Na2SO3 수용액을 처리함으로써 과량의 반응물과 부산물을 수용액 상으로 녹여 제거하여 하기 표 1과 같이 38-87%의 수득률로 순수한 방향족 요오드화합물을 제조하였다. 추가로, 재결정이나 관 크로마토그래피 방법을 적용하여 생성물을 정제하면 더 순수한 최종 생성물의 제조가 가능하다.The reaction product thus obtained was dissolved in Na 2 SO 3 Excess reactants and by-products were dissolved and removed by treating the aqueous solution to prepare a pure aromatic iodine compound in a yield of 38-87% as shown in Table 1 below. In addition, purification of the product by the application of recrystallization or tube chromatography allows for the preparation of a purer final product.

Figure 112007062809321-pat00001
Figure 112007062809321-pat00001

[표 1]TABLE 1

실시예Example 반응물(aryl amines)Aryl amines 생성물(aryl iodides)Aryl iodides 수득률 (%)Yield (%) 1One

Figure 112007062809321-pat00002
Figure 112007062809321-pat00002
Figure 112007062809321-pat00003
Figure 112007062809321-pat00003
 7272 22
Figure 112007062809321-pat00004
Figure 112007062809321-pat00004
Figure 112007062809321-pat00005
Figure 112007062809321-pat00005
 7272 33
Figure 112007062809321-pat00006
Figure 112007062809321-pat00006
Figure 112007062809321-pat00007
Figure 112007062809321-pat00007
 7575 44
Figure 112007062809321-pat00008
Figure 112007062809321-pat00008
Figure 112007062809321-pat00009
Figure 112007062809321-pat00009
 8787 55
Figure 112007062809321-pat00010
Figure 112007062809321-pat00010
Figure 112007062809321-pat00011
Figure 112007062809321-pat00011
 8787 66
Figure 112007062809321-pat00012
Figure 112007062809321-pat00012
Figure 112007062809321-pat00013
Figure 112007062809321-pat00013
 7979 77
Figure 112007062809321-pat00014
Figure 112007062809321-pat00014
Figure 112007062809321-pat00015
Figure 112007062809321-pat00015
 6363 88
Figure 112007062809321-pat00016
Figure 112007062809321-pat00016
Figure 112007062809321-pat00017
Figure 112007062809321-pat00017
 6767 99
Figure 112007062809321-pat00018
Figure 112007062809321-pat00018
Figure 112007062809321-pat00019
Figure 112007062809321-pat00019
 8080 1010
Figure 112007062809321-pat00020
Figure 112007062809321-pat00020
Figure 112007062809321-pat00021
Figure 112007062809321-pat00021
 7777 1111
Figure 112007062809321-pat00022
Figure 112007062809321-pat00022
Figure 112007062809321-pat00023
Figure 112007062809321-pat00023
 8585 1212
Figure 112007062809321-pat00024
Figure 112007062809321-pat00024
Figure 112007062809321-pat00025
Figure 112007062809321-pat00025
 7979 1313
Figure 112007062809321-pat00026
Figure 112007062809321-pat00026
Figure 112007062809321-pat00027
Figure 112007062809321-pat00027
 7070 1414
Figure 112007062809321-pat00028
Figure 112007062809321-pat00028
Figure 112007062809321-pat00029
Figure 112007062809321-pat00029
 8181 1515
Figure 112007062809321-pat00030
Figure 112007062809321-pat00030
Figure 112007062809321-pat00031
Figure 112007062809321-pat00031
 3838 16 16
Figure 112007062809321-pat00032
Figure 112007062809321-pat00032
Figure 112007062809321-pat00033
Figure 112007062809321-pat00033
 4141

본 발명의 기술을 사용하면 유기용매와 강한 무기산을 사용하지 않고, 상온에서 물-반죽 상태로 반응물을 일정시간 섞어 비교적 높은 수득률로, 방향족 아민화합물로부터 방향족 요오드화합물을 효과적으로 합성할 수 있다. 본 합성 기술은 적용방법이 간단하며, 반응조건은 온화하고 친환경적이다. 본 발명의 기술을 적용하면 전자를 주는 기는 물론 당기는 기로 치환된 다양한 방향족 아민화합물로부터 해당 방향족 요오드화합물을 성공적으로 합성할 수 있다. 또한 강산에 예민한 치환기를 갖는 방향족 아민화합물에도 본 발명 기술의 적용이 가능하다. Using the technique of the present invention, it is possible to effectively synthesize an aromatic iodine compound from an aromatic amine compound with a relatively high yield by mixing the reactants in water-dough at room temperature for a certain time without using an organic solvent and a strong inorganic acid. This synthesis technique is simple to apply and the reaction conditions are gentle and environmentally friendly. The application of the technique of the present invention can successfully synthesize the aromatic iodine compound from various aromatic amine compounds substituted with electron-gating groups and pulling groups. The present invention can also be applied to aromatic amine compounds having substituents sensitive to strong acids.

본 발명에 의해 합성된 방향족 요오드 화합물은 생체활성 물질 및 전자재료 또는 그 중간체의 합성 시 유용한 물질로 활용된다. The aromatic iodine compound synthesized by the present invention is utilized as a useful material in the synthesis of bioactive materials and electronic materials or intermediates thereof.

Claims (4)

하기 식 (I)의 방향족 아민화합물을 유기 용매를 사용하지 않고 금속요오드화물을 포함하는 반응물과 반응촉매로 p-톨루엔술폰산을 사용하여 상온에서 물-반죽 상태로 반응시키는 것을 특징으로 하는 하기 식(II)의 방향족 요오드화합물을 합성하는 방법:The aromatic amine compound of formula (I) is reacted in a water-dough state at room temperature using p- toluenesulfonic acid as a reaction catalyst with a reactant containing a metal iodide without using an organic solvent ( Method for synthesizing aromatic iodine compound of II):
Figure 112009005253435-pat00034
(I)
Figure 112009005253435-pat00034
(I)
Figure 112009005253435-pat00035
(II)
Figure 112009005253435-pat00035
(II) 상기 식 (I), 식(II)에서 R은 히드록실, 니트로, 할로겐, 시아노, 카르복실산, 페닐, -COCH3, -COONa, -OCH3로부터 선택된 하나 이상의 치환기이다. The formula (I), in formula (II) R is one or more substituents selected from hydroxyl, nitro, halo, cyano, carboxylic acid, phenyl, -COCH 3, -COONa, -OCH 3 . 하기 식 (III)의 아민화합물을 유기 용매를 사용하지 않고 금속요오드화물을 포함하는 반응물과 반응촉매로 p-톨루엔술폰산을 사용하여 상온에서 물-반죽 상태로 반응시키는 것을 특징으로 하는 하기 식(IV)의 요오드화합물을 합성하는 방법:The amine compound represented by the following formula (III) is reacted in a water-dough state at room temperature using p- toluenesulfonic acid as a reaction catalyst with a reactant containing a metal iodide without using an organic solvent. To synthesize an iodine compound:
Figure 112009005253435-pat00036
(III)
Figure 112009005253435-pat00036
(III)
Figure 112009005253435-pat00037
(IV)
Figure 112009005253435-pat00037
(IV) 제 1항에 있어서, 상기 금속요오드화물을 포함하는 반응물은 NaNO2 또는 KNO2 및 KI 또는 NaI인 것을 특징으로 하는 방향족 요오드화합물을 합성하는 방법.The reactant of claim 1, wherein the reactant comprising metal iodide is NaNO 2. Or KNO 2 and KI or NaI. 제 3 항에 있어서, 방향족 아민화합물 1당량에 대해 p-톨루엔술폰산은 1-5당량), NaNO2 또는 KNO2는 1-5당량, KI 또는 NaI는 1-5당량 사용하고 물은 200ml 이하의 소량으로 사용하는 것을 특징으로 하는 방향족 요오드화합물을 합성하는 방법.The amount of p- toluenesulfonic acid is 1-5 equivalents to 1 equivalent of the aromatic amine compound), NaNO 2 Or KNO 2 for 1-5 equivalents, KI or NaI for 1-5 equivalents, and water in a small amount of 200 ml or less.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960008644B1 (en) * 1987-08-18 1996-06-28 이스트만 코닥 컴퍼니 Process for the iodination of hydroxyaromatic and aminoaromatic compounds
US7138555B2 (en) 2004-04-20 2006-11-21 Xerox Corporation Process for preparing iodoaromatic compounds and using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR960008644B1 (en) * 1987-08-18 1996-06-28 이스트만 코닥 컴퍼니 Process for the iodination of hydroxyaromatic and aminoaromatic compounds
US7138555B2 (en) 2004-04-20 2006-11-21 Xerox Corporation Process for preparing iodoaromatic compounds and using the same

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