KR100730987B1 - Stereoselective preparation method of allylic sulfones for carotenoid synthesis - Google Patents

Stereoselective preparation method of allylic sulfones for carotenoid synthesis Download PDF

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KR100730987B1
KR100730987B1 KR1020060016458A KR20060016458A KR100730987B1 KR 100730987 B1 KR100730987 B1 KR 100730987B1 KR 1020060016458 A KR1020060016458 A KR 1020060016458A KR 20060016458 A KR20060016458 A KR 20060016458A KR 100730987 B1 KR100730987 B1 KR 100730987B1
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구상호
정세영
오정택
민재홍
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V17/00—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages
    • F21V17/10—Fastening of component parts of lighting devices, e.g. shades, globes, refractors, reflectors, filters, screens, grids or protective cages characterised by specific fastening means or way of fastening
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21—LIGHTING
    • F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
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Abstract

Provided are an allylic sulfone compound containing a benzene ring which is used for the synthesis of a carotene compound, a homoallylic alcohol compound containing a homoallylic sulfone group, and a method for preparing the allylic sulfone compound. The allylic sulfone compound is represented by the formula(1), wherein R1 and R2 are H, Me or Ph, respectively; R3 is OMe, SMe, Me, H or Cl, provided that R1 and R3 are H and R2 is H or Me is excluded. The homoallylic alcohol compound is represented by the formula(2), wherein R1 and R2 are H, Me or Ph, respectively; and R3 is OMe, SMe, Me, H or Cl. The method comprises the steps of reacting a haloallylic sulfone compound with a benzaldehyde compound containing various substituents in the presence of indium to prepare a homoallylic alcohol compound containing a homoallylic sulfone group; and reacting the homoallylic alcohol compound with the benzaldehyde compound containing various substituents under acidic condition to prepare the allylic sulfone compound by oxonia-Cope rearrangement.

Description

카로틴 화합물 합성에 사용되는 알릴릭 설폰 화합물의 입체 선택적인 제조 방법{Stereoselective preparation method of allylic sulfones for carotenoid synthesis}Stereoselective preparation method of allylic sulfones for carotenoid synthesis}

도 1은 치환체 R1이 메틸인 경우, 본 발명의 방법에 의해 제조되는 화학식 1의 X-선 결정구조(알콜기와 설폰기가 anti로 배열)를 나타내는 도면이고, 1 is a diagram showing an X-ray crystal structure (alcohol and sulfone groups arranged in anti ) of formula (1) prepared by the method of the present invention when the substituent R 1 is methyl,

도 2는 치환체 R1이 페닐인 경우, 본 발명의 방법에 의해 제조되는 화학식 1의 X-선 결정구조(알콜기와 설폰기가 syn으로 배열)를 나타내는 도면이다.FIG. 2 is a diagram showing an X-ray crystal structure (alcohol and sulfone groups arranged in syn ) of Chemical Formula 1 prepared by the method of the present invention when the substituent R 1 is phenyl.

본 발명은 카로틴 화합물의 합성에 사용되는 알릴릭 설폰 화합물과 그의 입체 선택적인 제조 방법에 관한 것으로서, 보다 상세하기로는, 설폰 화학을 이용하여 컨쥬게이트 폴리엔 사슬 구조로 이루어진 카로틴 화합물의 합성 시, 유용하게 이용되는 알릴릭 설폰 화합물(화학식 1), 이의 제조에 사용되는 신규의 중간체 화합물(화학식 2)과 그 제조방법, 상기 중간체 화합물을 이용한 화학식 1로 표시되는 알릴릭 설폰 화합물의 입체 선택적 제조방법에 관한 것이다.The present invention relates to an allyl sulfone compound used in the synthesis of carotene compounds and a stereoselective preparation method thereof, and more particularly, in the synthesis of a carotene compound composed of a conjugated polyene chain structure using sulfone chemistry. Allyl sulfone compound (Formula 1) to be used, a novel intermediate compound (Formula 2) used in the preparation thereof and a preparation method thereof, a stereoselective method for producing an allyl sulfone compound represented by the formula (1) using the intermediate compound It is about.

Figure 112006012413348-pat00001
Figure 112006012413348-pat00001

상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되며, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택된다. 단, R1과 R3가 모두 H 이고, R2가 H 이거나 Me인 경우는 제외한다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me, Ph, and R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl. Provided that both R 1 and R 3 are H and R 2 is H or Me.

Figure 112006012413348-pat00002
Figure 112006012413348-pat00002

상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되며, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택된다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me, Ph, and R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl.

베타-카로틴(β-carotene)으로 대표되는 카로틴 화합물들은 이중결합이 연속적으로 연결된 컨쥬게이트 폴리엔 체인(conjugated polyene chain)의 기본 구조를 가지며, 이로 인해 적황색을 나타내기 때문에 인체에 무해한 색소로서 산업적으로 널리 이용되고 있다. 또한 비타민 A의 전구체로서 조직의 생장과 분화, 시각 작용 및 암의 예방에도 효능이 있는 것으로 알려져, 건강보조제, 화장품 원료 및 식품 첨가제로 그 사용 범위가 확대되고 있다.Carotene compounds, represented by beta-carotene, have the basic structure of conjugated polyene chains in which double bonds are continuously connected, and because of this, they are reddish yellow and are industrially suitable as pigments that are harmless to the human body. It is widely used. In addition, as a precursor of vitamin A is known to be effective in the growth and differentiation of tissues, visual effects, and prevention of cancer, and its use as a health supplement, cosmetic raw materials and food additives is expanding.

베타-카로틴을 합성하는 대표적인 방법으로는 아세틸라이드(acetylide)를 이용하는 방법(Isler, O.; Lindlar, H.; Montavon, M.; Ruegg, R.; Zeller, P. Helv . Chim. Acta 1956, 39, 249-259), 비티히 반응(Wittig reaction)을 이용하는 방법(Wittig, G.; Pommer, H. German Patent 954,247; 1956)과, 쥴리아(Julia)에 의해 개발된 설폰 화학을 이용하는 방법(Koo, S.; Choi, H.; Ji, M.; Park, M. WO 00/27810; Koo, S.; Yang, J.-D.; Kim, J.-S.; Lee, S.; Park, M. WO 03/037,854) 등이 알려져 있다. 이들 중, 설폰 화학을 이용하는 방법은 생화학적 활성도가 큰 트랜스(trans) 구조의 이중결합을 생성하며, 합성 단계의 중간 생성물들이 매우 안정하고 결합 반응이 탁월하며, 이중결합 생성 시 얻어지는 부산물의 처리가 용이하다는 장점이 있다. Representative methods for synthesizing beta-carotene include acetylide (Isler, O .; Lindlar, H .; Montavon, M .; Ruegg, R .; Zeller, P. Helv . Chim. Acta 1956 , 39 , 249-259), using the Wittig reaction (Wittig, G .; Pommer, H. German Patent 954,247; 1956), and using the sulfone chemistry developed by Julia (Koo). , S .; Choi, H .; Ji, M .; Park, M. WO 00/27810; Koo, S .; Yang, J.-D .; Kim, J.-S .; Lee, S .; Park , M. WO 03 / 037,854). Among them, the method using sulfone chemistry produces trans-bonded double bonds with high biochemical activity, the intermediate products of the synthesis step are very stable, the binding reaction is excellent, and the treatment of by-products obtained when the double bonds are produced It has the advantage of being easy.

반응식 1에서 나타낸 바와 같이 설폰 화학을 이용하여 40개의 탄소로 이루어진 베타-카로틴의 합성을 위해서는 C15 알릴릭 설폰 화합물 A 두 분자와 C10 화합물 한 분자를 결합하여야 하며, 이를 위하여 화합물 B(WO 00/27810), 화합물 C(WO 03/037,854), 및 화합물 D(PCT/KR2005/002273)의 C10 유닛들이 개발되었고, 이들로부터 베타-카로틴의 효율적인 합성법이 보고되었다.As shown in Scheme 1, in order to synthesize beta-carotene composed of 40 carbons using sulfone chemistry, two molecules of C 15 allyl sulfone compound A and one molecule of C 10 compound should be combined. / 27810), Compound C (WO 03 / 037,854), and C 10 units of Compound D (PCT / KR2005 / 002273) have been developed from which an efficient synthesis of beta-carotene has been reported.

Figure 112006012413348-pat00003
Figure 112006012413348-pat00003

상기 반응식 1의 C15 알릴릭 설폰 화합물 A는 탄소 13개로 이루어진 베타-이오논(β-ionone)으로부터 제조될 수 있으며(Chabardes, P.; Decor, J. P.; Varagnat, J. Tetrahedron 1977, 33, 2799-2805), 설폰 화학을 이용한 베타-카로틴의 합성에 효율적으로 사용되었다. 한편, 화합물 A의 C15 알릴릭 설폰에서 싸이클로핵센 고리가 벤젠 고리로 바뀐 알릴릭 설폰 화합물(화학식 1)을 이용할 경우, 베타-카로틴의 양끝에 있는 싸이클로핵센 고리 대신 벤젠 고리를 함유하는 카로틴 화합물을 합성하게 될 것이다. 이와 같이 벤젠 고리를 함유하는 카로틴 화합물들은 라디칼(radical)들과 보다 효율적으로 반응하는 것으로 알려져 있기 때문에(Polyakov, N. E.; Kruppa, A. I.; Leshina, T. V.; Konovalova, T. A.; Kisper, L. D. Free Radical Biology & Medicine 2001, 31, 43-52) 매우 우수한 항산화제 및 라디칼 제거제로 사용될 수 있다. 또한, 이들은 비교적 안정하며, 전기화학적 특성을 지닌 물질로서(Liu, D.; Kispert, L. D. J. Phys . Chem . B 2001, 105, 975-980), 산업적으로도 널리 이용될 것으로 기대된다. 따라서, 벤젠 고리를 함유하는 카로틴 화합물의 합성을 위하여 화학식 1로 표시되는 알릴릭 설폰 화합물의 효율적인 제조 방법의 개발이 필요하게 되었다.C 15 allylic sulfone compound A of Scheme 1 may be prepared from β-ionone consisting of 13 carbons (Chabardes, P .; Decor, JP; Varagnat, J. Tetrahedron 1977 , 33 , 2799 -2805), and was efficiently used for the synthesis of beta-carotene using sulfone chemistry. On the other hand, when using the aryl sulfone compound (Chemical Formula 1) in which the cyclohexene ring is changed to the benzene ring in C 15 allyl sulfone of Compound A, a carotene compound containing a benzene ring instead of the cyclohexene ring at both ends of the beta-carotene Will be synthesized. Carotene compounds containing benzene rings are known to react more efficiently with radicals (Polyakov, NE; Kruppa, AI; Leshina, TV; Konovalova, TA; Kisper, LD Free). Radical Biology & Medicine 2001 , 31 , 43-52) It can be used as a very good antioxidant and radical scavenger. In addition, they are relatively stable, electrochemical materials (Liu, D .; Kispert, LD J. Phys . Chem . B 2001 , 105 , 975-980) and are expected to be widely used in industry. Therefore, it is necessary to develop an efficient method for producing an allylic sulfone compound represented by Chemical Formula 1 for the synthesis of a carotene compound containing a benzene ring.

본 발명이 이루고자하는 기술적 과제는, 상술한 바와 같이 우수한 항산화제 및 라디칼 제거제로 사용될 수 있고, 비교적 안정하며, 전기 화학적 특성을 지녀 산업적으로 응용가치가 높을 것으로 예상되는, 벤젠 고리를 함유하는 카로틴 화합물의 합성에 필요한 알릴릭 설폰 화합물(화학식 1)과 이들을 입체 선택적으로 합성하는 방법을 제공하는 것이다.The technical problem to be achieved by the present invention is a carotene compound containing a benzene ring, which can be used as an excellent antioxidant and radical scavenger as described above, is relatively stable, and has high electrochemical properties and is expected to have high industrial value. It is to provide an allylic sulfone compound (Formula 1) required for the synthesis of and a method for stereoselectively synthesizing them.

본 발명의 첫 번째 기술적 과제를 이루기 위하여 본 발명은 화학식 1로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the formula (1) to achieve the first technical problem of the present invention.

Figure 112006012413348-pat00004
Figure 112006012413348-pat00004

상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되며, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택된다. 단, R1과 R3가 모두 H 이고, R2가 H 이거나 Me인 경우는 제외한다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me, Ph, and R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl. Provided that both R 1 and R 3 are H and R 2 is H or Me.

본 발명의 두 번째 기술적 과제를 이루기 위하여 본 발명은 화학식 2로 표시되는 화합물을 제공한다.The present invention provides a compound represented by the formula (2) to achieve the second technical problem of the present invention.

Figure 112006012413348-pat00005
Figure 112006012413348-pat00005

상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되며, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택된다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me, Ph, and R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl.

발명의 세 번째 기술적 과제는, (a) 할로알릴릭 설폰 화합물 (E)를 인듐 중재 하에서 다양한 치환체를 함유하는 벤즈알데하이드 (F)와 반응시켜 화학식 2로 표시되는 호모알릴릭 설폰을 함유하는 호모알릴릭 알콜 화합물을 얻는 단계; 및 (b) 화학식 2의 호모알릴릭 알콜과 상기 벤즈알데하이드 (F)와의 산성 조건에서 옥소니아-코프 재배열(oxonia-Cope rearrangement) 반응을 통해 알릴릭 설폰 화합물을 합성하는 단계를 포함하는 것을 특징으로 하는 화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰 화합물의 제조 방법에 의해 이루어진다 (반응식 2).The third technical problem of the present invention is (a) homoallyl containing a homoallylic sulfone represented by the formula (2) by reacting a haloallylic sulfone compound (E) with benzaldehyde (F) containing various substituents under indium mediation. Obtaining a ric alcohol compound; And (b) synthesizing an allylic sulfone compound through an oxonia-Cope rearrangement reaction in an acidic condition of the homoallylic alcohol of Formula 2 and the benzaldehyde (F). It consists of the manufacturing method of the allyl sulfone compound containing the benzene ring represented by Formula (1).

Figure 112006012413348-pat00006
Figure 112006012413348-pat00006

상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되고, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택되며, X는 Cl, Br, I로 이루어진 군으로부터 선택된다.Wherein R 1 and R 2 are each selected from the group consisting of H, Me and Ph, R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl, and X is Cl, Br, I Selected from the group consisting of:

본 발명에 따른 화학식 1의 벤젠 고리를 함유하는 알릴릭 설폰 화합물은 상기 화합물 B, C, D 등의 C10 유닛과 결합하여 양끝에 벤젠 고리를 함유하는 카로틴 화합물의 합성에 사용될 수 있으며(반응식 1), 다음에 설명하는 바와 같이 할로알릴릭 설폰 화합물 (E)를 다양한 치환체를 갖는 벤즈알데하이드 화합물 (F)와 인듐의 중재 하에서 반응시켜 화학식 2의 호모알릴릭 알콜 화합물을 형성한 뒤, 상기 벤즈알데하이드 (F)와 산성 조건에서 옥소니아-코프 재배열 반응을 통해 제조하게 된다(반응식 2). The allylic sulfone compound containing the benzene ring of Formula 1 according to the present invention may be used in the synthesis of carotene compounds containing a benzene ring at both ends by combining with C 10 units such as compounds B, C, and D (Scheme 1) ), As described below, the haloallylic sulfone compound (E) is reacted with a benzaldehyde compound (F) having various substituents under an intermediate of indium to form a homoallylic alcohol compound of formula (2), and then the benzaldehyde It is prepared through the Oxonia-Cop rearrangement reaction under (F) and acidic conditions (Scheme 2).

상기 (a)단계의 인듐 중재 하에서 할로알릴릭 설폰 화합물 (E)와 벤즈알데하 이드 (F)의 반응은 물 또는 에틸알콜과 같은 극성 용매를 이용하거나, THF, DMF 또는 CH2Cl2와 같은 유기 용매와 물과의 혼합 용매를 사용하여, 20℃~120℃의 온도로 진행하게 되며, 부피 비 4:1의 물:THF 혼합 용매를 사용하는 것이 높은 수율의 결과물을 형성하는 점에서 바람직하다.The reaction of the haloallylic sulfone compound (E) and benzaldehyde (F) under the indium mediation of step (a) is carried out using a polar solvent such as water or ethyl alcohol, or THF, DMF or CH 2 Cl 2 Using a mixed solvent of an organic solvent and water, the mixture proceeds to a temperature of 20 ° C. to 120 ° C., and it is preferable to use a water: THF mixed solvent in a volume ratio of 4: 1 to form a high yield. .

상기 반응은 화합물 (E)의 탄소-할로겐 결합에 대한 인듐의 삽입(insertion)으로 알릴릭 메탈(인듐)을 형성하고, 알릴릭 재배열을 통하여 벤즈알데하이드 (F)에 첨가 반응으로 진행하여 호모알릴릭 알콜 화합물(화학식 2)을 형성하게 된다. 본 첨가반응은 입체 선택적으로 진행되는 것으로, 먼저 화합물 (E)의 이중결합의 입체 구조에 관계없이 인듐이 삽입되는 과정에서 좀더 안정된 트랜스 구조의 알릴릭 메탈(인듐)이 형성되며, 벤즈알데하이드 (F)와 반응으로 화학식 2의 호모알릴릭 알콜을 형성할 때에, 치환체 R1의 종류에 따라 OH 기와 PhSO2CH2 기의 상대적인 입체구조가 결정된다. 즉, R1 치환체가 메틸인 경우 13:1의 선택성으로 OH 기와 PhSO2CH2 기가 반대(anti) 방향으로 배열된 구조(도1 참조)가 얻어지며, R1 치환체가 페닐인 경우 13:1의 선택성으로 OH 기와 PhSO2CH2 기가 같은(syn) 방향으로 배열된 입체 구조(도2 참조)가 얻어지게 된다.The reaction forms an allyl metal (indium) by insertion of indium to the carbon-halogen bond of compound (E), and proceeds to the addition reaction to benzaldehyde (F) via allyl rearrangement to homoallyl It forms a lig alcohol compound (Formula 2). This addition reaction proceeds stereoselectively. First, regardless of the stereostructure of the double bond of compound (E), more stable trans-allylic allyl metal (indium) is formed in the process of indium insertion, and benzaldehyde (F When the homoallylic alcohol of Formula 2 is formed by reaction with), the relative stereostructure of the OH group and the PhSO 2 CH 2 group is determined according to the type of the substituent R 1 . That is, when the R 1 substituent is methyl, a selectivity of 13: 1 gives a structure in which the OH group and the PhSO 2 CH 2 group are arranged in the anti direction (see FIG. 1), and when the R 1 substituent is phenyl 13: 1 The selectivity of gives a three-dimensional structure (see Fig. 2) in which OH groups and PhSO 2 CH 2 groups are arranged in the same ( syn ) direction.

인듐 대신에 마그네슘(Mg), 아연(Zn), 주석(Sn)과 같은 금속의 중재 하에서 상기의 할로알릴릭 설폰 화합물(E)과 벤즈알데하이드(F)의 결합 반응을 진행할 경우, 마그네슘을 이용한 경우에는 반응이 전혀 진행되지 않으며, 아연과 주석을 이 용하는 경우에는 결합 반응물인 호모알릴릭 알콜 화합물(화학식 2)이 소량(~20% 수율) 얻어지게 된다. In the case of the reaction of combining the haloallylic sulfone compound (E) and benzaldehyde (F) under the intervention of metals such as magnesium (Mg), zinc (Zn) and tin (Sn) instead of indium, when magnesium is used The reaction does not proceed at all, and in the case of using zinc and tin, a small amount (˜20% yield) of the homoallylic alcohol compound (Formula 2) as a binding reactant is obtained.

상기 (b)단계의 호모알릴릭 알콜(화학식 2)과 벤즈알데하이드(F)의 옥소니아-코프(oxonia-Cope) 재배열 반응(rearrangement reaction)은 ZnCl2, BF3·OEt2, ZnBr2 등의 루이스산(Lewis acid), 파라-톨루엔설폰산(p-toluenesulfonic acid), 켐포설폰산(10-camphorsulfonic acid) 등의 유기산 및 HCl 수용액과 같은 무기산(mineral acid)을 이용하고 CH2Cl2, ClCH2CH2Cl, benzene, toluene 등의 유기용매 또는 물(H2O)에서 40℃~120℃의 온도로 진행하는 것이 바람직하다.The oxonia-Cope rearrangement reaction of the homoallylic alcohol (Formula 2) and benzaldehyde (F) in step (b) is ZnCl 2 , BF 3 · OEt 2 , ZnBr 2, and the like. of a Lewis acid (Lewis acid), p-toluenesulfonic acid using a (p -toluenesulfonic acid), Chem laid acid (10-camphorsulfonic acid) acid and an inorganic acid (mineral acid) such as HCl and an aqueous solution, such as CH 2 Cl 2, In an organic solvent such as ClCH 2 CH 2 Cl, benzene, toluene or water (H 2 O), it is preferable to proceed to a temperature of 40 ℃ ~ 120 ℃.

산성 조건에서 화학식 2의 호모알릴릭 알콜은 벤즈알데하이드(F)와 반응하여 아세탈을 형성하고, 물을 제거하며 (G) 구조의 옥소카베니움 이온(oxocarbenium ion)을 형성하게 된다. 구조 (G)의 옥소카베니움 이온은 옥소니아-코프(oxonia-Cope)의 시그마트로픽 재배열 반응(sigmatropic rearrangement reaction)을 통하여 구조 (H)의 옥소카베니움 이온을 형성하고, 여기서 벤즈알데하이드를 제거하여 화학식 1로 표시되는 알릴릭 설폰 화합물을 형성하게 된다(반응식 3).Under acidic conditions, the homoallylic alcohol of Formula 2 reacts with benzaldehyde (F) to form acetal, remove water and form oxocarbenium ion of (G) structure. The oxocarbenium ions of structure (G) form the oxocarbenium ions of structure (H) through a sigmatropic rearrangement reaction of oxonia-Cope, where benzaldehyde To form an allyl sulfone compound represented by Formula 1 (Scheme 3).

Figure 112006012413348-pat00007
Figure 112006012413348-pat00007

상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택된다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me and Ph.

옥소니아-코프 재배열 반응도 입체 선택적으로 진행되어, 화학식 2의 알콜기와 설폰기가 반대 방향으로 배열된 안티(anti) 입체 이성질체를 이용하여 반응을 진행하는 경우에는 R1과 R2를 함유하는 이중결합이 트랜스(trans) 구조를 갖게 되며, 화학식 2의 알콜기와 설폰기가 같은 방향으로 배열된 씬(syn) 입체 이성질체를 이용하여 반응하면 씨스(cis) 구조의 이중결합을 형성하게 된다.The oxonia-copper rearrangement reaction is also stereosterically selected, and double bonds containing R 1 and R 2 are used when the reaction is carried out using anti stereoisomers in which alcohol groups and sulfone groups of formula (2) are arranged in opposite directions. This has a trans structure, and when the alcohol group and the sulfone group of Formula 2 are reacted using the syn stereo isomers arranged in the same direction, a double bond of cis structure is formed.

한편, 호모알릴릭 알콜(화학식 2)의 옥소니아-코프 재배열 반응 시, 화학식 2의 제조에 사용되었던 벤즈알데하이드 (F)와는 다른 종류의 벤즈알데하이드를 사용할 수도 있으나, 반응의 수율을 고려하여 볼 때 같은 종류의 벤즈알데하이드 (F)를 사용하는 것이 바람직하다.Meanwhile, in the oxonia-copper rearrangement reaction of homoallylic alcohol (Formula 2), a benzaldehyde (F) different from the benzaldehyde (F) used in the preparation of Formula 2 may be used, but considering the yield of the reaction, It is preferable to use the same kind of benzaldehyde (F).

이하, 본 발명을 실시 예를 들어 상세히 설명하기로 하되, 본 발명이 하기 실시 예로만 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited only to the following Examples.

실시 예 1-1. 2- 벤젠설포닐메틸 -2- 메틸 -1- 페닐 -3- 부텐 -1-올: 화학식 2의 R 1 = 메틸 , R 2 = 수소, R 3 = 수소인 경우. Example 1-1. 2- benzenesulfonylmethyl- 2 - methyl - 1 - phenyl- 3- butene -1-ol: where R 1 = methyl , R 2 = hydrogen, R 3 = hydrogen in formula 2 .

트랜스 구조의 1-벤젠설포닐-4-클로로-2-메틸-2-부텐(화합물 E의 R1 = 메틸, R2 = 수소, X = 염소인 경우) 0.31 g(1.25 mmol)을 THF 2 ㎖에 녹인 용액에 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.16 g(1.50 mmol), 인듐 0.16 g(1.38 mmol), 그리고 물 8 ㎖를 첨가한 다음 100 ℃로 2.5 시간 동안 가열한다. 상기 용액을 상온으로 식히고, CH2Cl2로 묽힌 뒤, 1M HCl 수용액으로 씻은 다음, 무수 Na2SO4로 수분을 제거한다. 상기 혼합물을 필터 페이퍼로 거른 뒤, 감압 하에 농축하고, 그 결과물을 핵산으로 씻어 정제하여 흰색 고체의 화학식 2로 표시되는 호모알릴릭 알콜 0.39 g(1.23 mmol, anti:syn = 13:1)을 98%의 수율로 얻는다.2 ml of THF 0.31 g (1.25 mmol) of 1-benzenesulfonyl-4-chloro-2-methyl-2-butene having trans structure (if R 1 = methyl, R 2 = hydrogen, X = chlorine of Compound E) To this solution was added 0.16 g (1.50 mmol) of benzaldehyde (if R 3 = hydrogen of compound F), 0.16 g (1.38 mmol) of indium, and 8 ml of water, and then heated to 100 ° C. for 2.5 hours. The solution is cooled to room temperature, diluted with CH 2 Cl 2 , washed with 1M HCl aqueous solution, and then dried with anhydrous Na 2 SO 4 . The mixture was filtered through filter paper, concentrated under reduced pressure, and the resultant was washed with nucleic acid to purify the mixture to obtain 0.39 g (1.23 mmol, anti : syn = 13: 1) of homoallylic alcohol represented by the formula (2) as a white solid. Obtained in% yield.

데이터(anti): 1H NMR δ 1.31 (s, 3H), 1.60 (br s, 1H), 3.15 (ABq, J = 14.1 Hz, 1H), 3.54 (ABq, J = 14.1 Hz, 1H), 4.92 (dd, J = 17.6, 0.8 Hz, 1H), 5.01 (s, 1H), 5.11 (d, J = 10.8 Hz, 1H), 5.95 (dd, J = 17.6, 10.8 Hz, 1H), 7.20~7.35 (m, 5H), 7.52~7.70 (m, 3H), 7.86~7.96 (m, 2H) ppm; 13C NMR δ 19.7, 46.3, 62.6, 78.4, 115.9, 127.6, 127.7, 127.9, 128.1, 129.3, 133.6, 139.6, 139.9, 141.3 ppm; IR (KBr) 3503, 1541, 1305, 1266, 1148 cm-1; HRMS (FAB+) cacld for C18H19O2S (C18H20O3S ―OH) 299.1106, found 299.1105. Data ( anti ): 1 H NMR δ 1.31 (s, 3H), 1.60 (br s, 1H), 3.15 (ABq, J = 14.1 Hz, 1H), 3.54 (ABq, J = 14.1 Hz, 1H), 4.92 ( dd, J = 17.6, 0.8 Hz, 1H), 5.01 (s, 1H), 5.11 (d, J = 10.8 Hz, 1H), 5.95 (dd, J = 17.6, 10.8 Hz, 1H), 7.20-7.35 (m , 5H), 7.52-7.70 (m, 3H), 7.86-7.96 (m, 2H) ppm; 13 C NMR δ 19.7, 46.3, 62.6, 78.4, 115.9, 127.6, 127.7, 127.9, 128.1, 129.3, 133.6, 139.6, 139.9, 141.3 ppm; IR (KBr) 3503, 1541, 1305, 1266, 1148 cm −1 ; HRMS (FAB + ) cacld for C 18 H 19 O 2 S (C 18 H 20 O 3 S —OH) 299.1106, found 299.1105.

데이터(syn): 1H NMR δ 1.15 (s, 3H), 3.12 (ABq, J = 13.9 Hz, 1H), 3.58 (ABq, J = 13.9 Hz, 1H), 4.93 (dd, J = 17.4, 0.8 Hz, 1H), 5.03 (s, 1H), 6.29 (dd, J = 17.3, 10.9 Hz, 1H) ppm.Data ( syn ): 1 H NMR δ 1.15 (s, 3H), 3.12 (ABq, J = 13.9 Hz, 1H), 3.58 (ABq, J = 13.9 Hz, 1H), 4.93 (dd, J = 17.4, 0.8 Hz , 1H), 5.03 (s, 1H), 6.29 (dd, J = 17.3, 10.9 Hz, 1H) ppm.

인듐 중재 하에서의 상기 화합물 E(R1 = Me, R2 = H, X = Cl)와 벤즈알데하이드 F(R3 = H)의 결합 반응을 여러 다양한 용매를 사용하여 진행하여 화학식 2의 화합물을 얻을 수 있었으며, 그 결과를 다음의 표에 요약 정리하였다.The reaction of the compound E (R 1 = Me, R 2 = H, X = Cl) and benzaldehyde F (R 3 = H) under indium mediation can be carried out using various solvents to obtain a compound of formula (2). The results are summarized in the following table.

entry entry 화합물 E g (mmol)Compound E g (mmol) 화합물 F g (mmol)Compound F g (mmol) Indium g (mmol)Indium g (mmol) 용매 (㎖)Solvent (ml) 온도 ℃Temperature ℃ 시간 hTime h 화학식 2Formula 2 수율g(%)Yield g (%) anti:syn anti : syn 1One 0.44 (1.81)0.44 (1.81) 0.16 (1.51)0.16 (1.51) 0.19 (1.66)0.19 (1.66) EtOH (10)EtOH (10) 9090 1111 0.26 (55)0.26 (55) 4:14: 1 22 0.44 (1.80)0.44 (1.80) 0.16 (1.50)0.16 (1.50) 0.19 (1.65)0.19 (1.65) H2O (10)H 2 O (10) 100100 88 0.29 (62)0.29 (62) 10:110: 1 33 0.43 (1.75)0.43 (1.75) 0.16 (1.46)0.16 (1.46) 0.18 (1.61)0.18 (1.61) EtOH (2) H2O (8)EtOH (2) H 2 O (8) 100100 33 0.37 (81)0.37 (81) 10:110: 1 44 0.58 (2.39)0.58 (2.39) 0.21 (1.99)0.21 (1.99) 0.25 (2.19)0.25 (2.19) CH2Cl2 (2) H2O (8)CH 2 Cl 2 (2) H 2 O (8) 100100 1111 0.54 (86)0.54 (86) 10:110: 1 55 0.39 (1.61)0.39 (1.61) 0.14 (1.34)0.14 (1.34) 0.17 (1.47)0.17 (1.47) DMF (2) H2O (8)DMF (2) H 2 O (8) 100100 3.53.5 0.38 (90)0.38 (90) 13:113: 1 66 0.37 (1.50)0.37 (1.50) 0.13 (1.25)0.13 (1.25) 0.16 (1.38)0.16 (1.38) THF (2) H2O (8)THF (2) H 2 O (8) 100100 2.52.5 0.39 (98)0.39 (98) 13:113: 1 77 0.44 (1.80)0.44 (1.80) 0.16 (1.50)0.16 (1.50) 0.19 (1.65)0.19 (1.65) THF (2) H2O (8)THF (2) H 2 O (8) 2525 2424 0.32 (68)0.32 (68) 13:113: 1 88 0.31 (1.27)0.31 (1.27) 0.16 (1.52)0.16 (1.52) 0.16 (1.40)0.16 (1.40) THF (8) H2O (0.14 g)THF (8) H 2 O (0.14 g) 6060 3.53.5 0.20 (50)0.20 (50) 3:13: 1

실시 예 1-2. (5- 벤젠설포닐 -4- 메틸 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 메틸, R 2 = 수소, R 3 = 수소인 경우. Example 1-2. (5- Benzenesulfonyl - 4- methyl -1,3- pentadienyl ) benzene: when R 1 of formula 1 = methyl, R 2 = hydrogen, R 3 = hydrogen .

상기 실시 예 1-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.36 g(1.14 mmol)을 벤젠 10 ㎖에 녹이고 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.13 g(1.25 mmol)과 10-캠포설폰산 0.29 g(1.25 mmol)을 더한다. 반응 혼합물을 100 ℃로 3.5시간 동안 가열한 뒤, 실온으로 식혀 CH2Cl2로 묽히고, 물로 씻은 다음, 무수 Na2SO4로 수분을 제거한다. 상기 혼합물을 필터 페이퍼로 거른 뒤, 감압 하에 농축하고, 그 결과물을 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 트랜스 구조의 이중결합을 함유하는 화학식 1로 표시되는 알릴릭 설폰 0.24 g(0.80 mmol)을 70%의 수율로 얻는다.0.36 g (1.14 mmol) of the homoallylic alcohol of Chemical Formula 2, which is the result of Example 1-1, was dissolved in 10 ml of benzene, and 0.13 g (1.25 mmol) of benzaldehyde (if R 3 = hydrogen of Compound F) and 10- Add 0.29 g (1.25 mmol) of camphorsulfonic acid. The reaction mixture is heated to 100 ° C. for 3.5 h, cooled to rt, diluted with CH 2 Cl 2 , washed with water and then dried with anhydrous Na 2 SO 4 . The mixture was filtered through filter paper, concentrated under reduced pressure, and the resultant was purified by chromatography using silica gel, to obtain 0.24 g (0.80 mmol) of allylic sulfone represented by the formula (1) containing a double bond of a trans structure. Obtained in 70% yield.

데이터: 1H NMR δ 1.96 (s, 3H), 3.84 (s, 2H), 5.82 (d, J = 10.8 Hz, 1H), 6.38 (d, J = 15.6 Hz, 1H), 6.88 (dd, J = 15.6, 10.8 Hz, 1H), 7.21~7.39 (m, 5H), 7.52~7.67 (m, 3H), 7.85~7.88 (m, 2H) ppm; 13C NMR δ 17.7, 66.7 123.9, 125.2, 126.5, 127.9, 128.5, 128.7, 129.1, 133.7, 134.2, 134.6, 137.0, 138.5 ppm; IR (KBr) 1447, 1307, 1143 cm-1; HRMS (FAB+) cacld for C18H18O2S 298.1027, found 298.1021.Data: 1 H NMR δ 1.96 (s, 3H), 3.84 (s, 2H), 5.82 (d, J = 10.8 Hz, 1H), 6.38 (d, J = 15.6 Hz, 1H), 6.88 (dd, J = 15.6, 10.8 Hz, 1H), 7.21-7.39 (m, 5H), 7.52-77.6 (m, 3H), 7.85-7.88 (m, 2H) ppm; 13 C NMR δ 17.7, 66.7 123.9, 125.2, 126.5, 127.9, 128.5, 128.7, 129.1, 133.7, 134.2, 134.6, 137.0, 138.5 ppm; IR (KBr) 1447, 1307, 1143 cm −1 ; HRMS (FAB + ) cacld for C 18 H 18 O 2 S 298.1027, found 298.1021.

상기 실시 예 1-1의 결과물인 화학식 2의 호모알릴릭 알콜(R1 = Me, R2 = H, R3 = H)과 벤즈알데하이드 F(R3 = H)와의 옥소니아-코프 재배열 반응을 다양한 산 조건에서 시도하여 화학식 1의 화합물을 얻을 수 있었으며, 그 결과를 다음의 표에 요약 정리하였다. 이때 얻어지는 화학식 1의 알릴릭 설폰 화합물(R1 = Me, R2 = H, R3 = H)은 모두 트랜스 구조의 이중 결합을 함유하게 된다.Oxonia-copper rearrangement of homoallylic alcohol of formula 2 (R 1 = Me, R 2 = H, R 3 = H) and benzaldehyde F (R 3 = H), which is a result of Example 1-1 Was attempted under various acid conditions to obtain the compound of Formula 1, and the results are summarized in the following table. The allylic sulfone compound of formula 1 (R 1 = Me, R 2 = H, R 3 = H) obtained at this time all contain a double bond of a trans structure.

entry entry 화학식 2 g (mmol)Formula 2 g (mmol) 화합물 F g (mmol)Compound F g (mmol) 산 g (mmol)Acid g (mmol) 용매 (㎖)Solvent (ml) 온도 ℃Temperature ℃ 시간 hTime h 화학식 1 수율 g (%)Formula 1 yield g (%) 1One 0.34 (1.06)0.34 (1.06) 0.12 (1.16)0.12 (1.16) ZnCl2 0.16 (1.16)ZnCl 2 0.16 (1.16) CH2Cl2 (10)CH 2 Cl 2 (10) 4040 88 0.025 (8)0.025 (8) 22 0.34 (1.09)0.34 (1.09) 0.13 (1.20)0.13 (1.20) ZnCl2 0.16 (1.20)ZnCl 2 0.16 (1.20) ClCH2CH2Cl (10)ClCH 2 CH 2 Cl (10) 8080 55 0.045 (14)0.045 (14) 33 0.42 (1.33)0.42 (1.33) 0.16 (1.46)0.16 (1.46) BF3·OEt2 0.21 (1.46) BF 3 · OEt 2 0.21 (1.46 ) CH2Cl2 (10)CH 2 Cl 2 (10) 4040 33 0.123 (31)0.123 (31) 44 0.35 (1.12)0.35 (1.12) 0.13 (1.23)0.13 (1.23) ZnBr2 0.28 (1.23)ZnBr 2 0.28 (1.23) CH2Cl2 (10)CH 2 Cl 2 (10) 4040 88 0.103 (31)0.103 (31) 55 0.29 (0.93)0.29 (0.93) 0.11 (1.02)0.11 (1.02) 3 M HCl 20 mL (60)3 M HCl 20 mL (60) ―― 100100 1010 0.083 (37)0.083 (37) 66 0.36 (1.15)0.36 (1.15) 0.13 (1.27)0.13 (1.27) p-TsOH 0.11 (0.58) p -TsOH 0.11 (0.58) benzene (10)benzene (10) 8080 33 0.103 (30)0.103 (30) 77 0.32 (1.02)0.32 (1.02) 0.12 (1.13)0.12 (1.13) CSA 0.12 (0.51)CSA 0.12 (0.51) CH2Cl2 (10)CH 2 Cl 2 (10) 4040 1212 0.055 (18)0.055 (18) 88 0.35 (1.09)0.35 (1.09) 0.13 (1.20)0.13 (1.20) CSA 0.13 (0.55)CSA 0.13 (0.55) ClCH2CH2Cl (10)ClCH 2 CH 2 Cl (10) 8080 1212 0.150 (46)0.150 (46) 99 0.56 (1.75)0.56 (1.75) 0.20 (1.93)0.20 (1.93) CSA 0.45 (1.93)CSA 0.45 (1.93) ClCH2CH2Cl (10)ClCH 2 CH 2 Cl (10) 8080 2020 0.324 (62)0.324 (62) 1010 0.36 (1.14)0.36 (1.14) 0.13 (1.25)0.13 (1.25) CSA 0.29 (1.25)CSA 0.29 (1.25) benzene (10)benzene (10) 8080 3.53.5 0.238 (70)0.238 (70)

실시 예 2-1. 2- 벤젠설포닐메틸 -1-(4- 메톡시페닐 )-2- 메틸 -3- 부텐 -1-올: 화학식 2의 R 1 = 메틸 , R 2 = 수소, R 3 = 메톡시인 경우. Example 2-1. 2-benzenesulfonyl-1- (4-methoxyphenyl) -2-methyl-3-buten-1-ol: In case of R 1 = methyl, R 2 = hydrogen, R 3 = methoxy in the formula (2).

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-클로로-2-메틸-2-부텐(화합물 E의 R1 = 메틸, R2 = 수소, X = 염소인 경우) 0.44 g(1.79 mmol)을 THF 2 ㎖에 녹인 용액에 파라-메톡시벤즈알데하이드(화합물 F의 R3 = 메톡시인 경우) 0.22 g(1.62 mmol), 인듐 0.20 g(1.79 mmol), 그리고 물 8 ㎖를 첨가한 다음 100 ℃로 3 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 0.45 g(1.30 mmol, anti:syn = 13:1) 을 80%의 수율로 얻는다.In the same manner as in Example 1-1, when 1-benzenesulfonyl-4-chloro-2-methyl-2-butene having a trans structure (R 1 = methyl, R 2 = hydrogen, X = chlorine of Compound E) ) 0.22 g (1.62 mmol) of para-methoxybenzaldehyde (if R 3 = methoxy of Compound F), 0.20 g (1.79 mmol) of indium, and water in a solution of 0.44 g (1.79 mmol) in 2 mL of THF. 8 ml was added, followed by reaction at 100 ° C. for 3 hours, followed by purification by silica gel chromatography to obtain 0.45 g (1.30 mmol, anti : syn = 13: 1) of homoallylic alcohol represented by Chemical Formula 2 at 80%. To yield.

데이터(anti): 1H NMR δ 1.28 (s, 3H), 2.64 (br s, 1H), 3.15 (d, J = 14.1 Hz, 1H), 3.51 (d, J = 14.1 Hz, 1H), 3.80 (s, 3H), 4.93 (d, J = 17.6 Hz, 1H), 4.94 (s, 1H), 5.12 (d, J = 10.8 Hz, 1H), 5.94 (dd, J = 17.6, 10.8 Hz, 1H), 6.83 (d, J = 8.6 Hz, 2H), 7.22 (d, J = 8.6 Hz, 2H), 7.53~7.67 (m, 3H), 7.89~7.93 (m, 2H) ppm; 13C NMR δ 19.6, 46.4, 55.2, 62.7, 78.1, 113.0, 115.9, 127.8, 129.2, 129.3, 131.6, 133.6, 140.0, 141.3, 159.2 ppm; IR (KBr) 3503, 1513, 1447, 1305, 1249, 1147 cm-1; HRMS (FAB+) cacld for C19H21O3S (C19H22O4S - OH) 329.1211, found 329.1205.Data ( anti ): 1 H NMR δ 1.28 (s, 3H), 2.64 (br s, 1H), 3.15 (d, J = 14.1 Hz, 1H), 3.51 (d, J = 14.1 Hz, 1H), 3.80 ( s, 3H), 4.93 (d, J = 17.6 Hz, 1H), 4.94 (s, 1H), 5.12 (d, J = 10.8 Hz, 1H), 5.94 (dd, J = 17.6, 10.8 Hz, 1H), 6.83 (d, J = 8.6 Hz, 2H), 7.22 (d, J = 8.6 Hz, 2H), 7.53-7.67 (m, 3H), 7.89-7.83 (m, 2H) ppm; 13 C NMR δ 19.6, 46.4, 55.2, 62.7, 78.1, 113.0, 115.9, 127.8, 129.2, 129.3, 131.6, 133.6, 140.0, 141.3, 159.2 ppm; IR (KBr) 3503, 1513, 1447, 1305, 1249, 1147 cm −1 ; HRMS (FAB + ) cacld for C 19 H 21 O 3 S (C 19 H 22 O 4 S -OH) 329.1211, found 329.1205.

데이터(syn): 1H NMR δ 1.15 (s, 3H), 3.10 (d, J = 13.6 Hz, 1H), 3.55 (d, J = 13.6 Hz, 1H), 6.25 (dd, J = 17.6, 11.0 Hz, 1H) ppm.Data ( syn ): 1 H NMR δ 1.15 (s, 3H), 3.10 (d, J = 13.6 Hz, 1H), 3.55 (d, J = 13.6 Hz, 1H), 6.25 (dd, J = 17.6, 11.0 Hz , 1H) ppm.

실시 예 2-2. 4- 메톡시 -1-(5- 벤젠설포닐 -4- 메틸 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 메틸 , R 2 = 수소, R 3 = 메톡시인 경우. Example 2-2. 4-Methoxy-1- (5-benzenesulfonylamino-4-methyl-1,3-pentadienyl) benzene: In case of R 1 = methyl, R 2 = hydrogen, R 3 = methoxy in the formula (I).

상기 실시 예 1-2와 같은 방법으로, 실시 예 2-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.35 g(1.00 mmol)을 벤젠 10 ㎖에 녹이고 파라-메톡시벤즈알데하이드(화합물 F의 R3 = 메톡시인 경우) 0.14 g(1.00 mmol)과 10-캠포설폰산 0.26 g(1.10 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 1시간 동안 반응시킨 뒤, 실리 카겔을 이용한 크로마토그래피의 방법으로 정제하여 트랜스 구조의 이중결합을 함유하는 화학식 1로 표시되는 알릴릭 설폰 0.26 g(0.80 mmol)을 80%의 수율로 얻는다.In the same manner as in Example 1-2, 0.35 g (1.00 mmol) of the homoallylic alcohol of Formula 2, which is the result of Example 2-1, was dissolved in 10 ml of benzene and para-methoxybenzaldehyde (R 3 of Compound F = Methoxy) 0.14 g (1.00 mmol) and 0.26 g (1.10 mmol) of 10-camphorsulfonic acid were added, and then the reaction mixture was reacted at 100 ° C. for 1 hour, followed by chromatography using silica gel. Purification yields 0.26 g (0.80 mmol) of allyl sulfone represented by the formula (1) containing a double bond of a trans structure in a yield of 80%.

데이터: 1H NMR δ 1.94 (s, 3H), 3.80 (s, 3H), 3.82 (s, 2H), 5.79 (d, J = 10.8 Hz, 1H), 6.33 (d, J = 15.4 Hz, 1H), 6.74 (dd, J = 15.4, 11.0 Hz, 1H), 6.84 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 8.8 Hz, 2H), 7.46~7.66 (m, 3H), 7.84~7.87 (m, 2H) ppm; 13C NMR δ 17.5, 55.2, 66.7, 114.0, 121.9, 123.7, 127.7, 128.4, 129.0, 129.7, 133.6, 133.7, 134.7, 138.4, 159.4 ppm; IR (KBr) 1509, 1446, 1305, 1249, 1142 cm-1; HRMS (FAB+) calcd for C19H20O3S 328.1133, found 328.1149.Data: 1 H NMR δ 1.94 (s, 3H), 3.80 (s, 3H), 3.82 (s, 2H), 5.79 (d, J = 10.8 Hz, 1H), 6.33 (d, J = 15.4 Hz, 1H) , 6.74 (dd, J = 15.4, 11.0 Hz, 1H), 6.84 (d, J = 8.8 Hz, 2H), 7.31 (d, J = 8.8 Hz, 2H), 7.46-7.62 (m, 3H), 7.84- 7.87 (m, 2 H) ppm; 13 C NMR δ 17.5, 55.2, 66.7, 114.0, 121.9, 123.7, 127.7, 128.4, 129.0, 129.7, 133.6, 133.7, 134.7, 138.4, 159.4 ppm; IR (KBr) 1509, 1446, 1305, 1249, 1142 cm −1 ; HRMS (FAB + ) calcd for C 19 H 20 O 3 S 328.1133, found 328.1149.

실시 예 3-1. 2- 벤젠설포닐메틸 -2- 메틸 -1-(4- 메틸페닐 )-3- 부텐 -1-올: 화학식 2의 R 1 = 메틸 , R 2 = 수소, R 3 = 메틸인 경우. Example 3-1. 2-benzenesulfonyl-2-methyl-1- (4-methylphenyl) -3-buten-1-ol: In case of R 1 = methyl, R 2 = hydrogen, R 3 = methyl in the formula (2).

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-클로로-2-메틸-2-부텐(화합물 E의 R1 = 메틸, R2 = 수소, X = 염소인 경우) 0.39 g(1.58 mmol)을 THF 2 ㎖에 녹인 용액에 파라-메틸벤즈알데하이드(화합물 F의 R3 = 메틸인 경우) 0.16 g(1.32 mmol), 인듐 0.17 g(1.45 mmol), 그리고 물 8 ㎖를 첨가한 다음 100 ℃로 4 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 0.39 g(1.18 mmol, anti:syn = 13:1)을 90%의 수율로 얻는다.In the same manner as in Example 1-1, when 1-benzenesulfonyl-4-chloro-2-methyl-2-butene having a trans structure (R 1 = methyl, R 2 = hydrogen, X = chlorine of Compound E) ) 0.16 g (1.32 mmol) of para-methylbenzaldehyde (if R 3 = methyl) of Compound F, 0.17 g (1.45 mmol), and 8 mL of water in a solution of 0.39 g (1.58 mmol) in 2 mL of THF. The reaction was carried out at 100 ° C. for 4 hours, and then purified by silica gel chromatography to obtain 0.39 g (1.18 mmol, anti : syn = 13: 1) of homoallylic alcohol represented by Chemical Formula 2 in 90% yield. Get into.

데이터(anti): 1H NMR δ 1.29 (s, 3H), 2.32 (s, 3H), 2.71 (br d, J = 3.3 Hz, 1H), 3.16 (d, J = 14.2 Hz, 1H), 3.51 (d, J = 14.2 Hz, 1H), 4.92 (d, J = 17.4 Hz, 1H), 4.92 (br s, 1H), 5.11 (d, J = 10.8 Hz, 1H), 5.93 (dd, J = 17.4, 10.8 Hz, 1H), 7.09 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.25~7.66 (m, 3H), 7.88~7.92 (m, 2H) ppm; 13C NMR δ 19.5, 21.1, 46.2, 62.6, 78.3, 115.8, 127.7, 127.9, 128.3, 129.2, 133.5, 136.5, 137.5, 139.9, 141.3 ppm; IR (KBr) 3503, 1447, 1306, 1147 cm-1; HRMS (FAB+) calcd for C19H21O2S (C19H22O3S - OH) 313.1262, found 313.1257.Data ( anti ): 1 H NMR δ 1.29 (s, 3H), 2.32 (s, 3H), 2.71 (br d, J = 3.3 Hz, 1H), 3.16 (d, J = 14.2 Hz, 1H), 3.51 ( d, J = 14.2 Hz, 1H), 4.92 (d, J = 17.4 Hz, 1H), 4.92 (br s, 1H), 5.11 (d, J = 10.8 Hz, 1H), 5.93 (dd, J = 17.4, 10.8 Hz, 1H), 7.09 (d, J = 8.1 Hz, 2H), 7.17 (d, J = 8.1 Hz, 2H), 7.25-7.62 (m, 3H), 7.88-7.82 (m, 2H) ppm; 13 C NMR δ 19.5, 21.1, 46.2, 62.6, 78.3, 115.8, 127.7, 127.9, 128.3, 129.2, 133.5, 136.5, 137.5, 139.9, 141.3 ppm; IR (KBr) 3503, 1447, 1306, 1147 cm −1 ; HRMS (FAB + ) calcd for C 19 H 21 O 2 S (C 19 H 22 O 3 S -OH) 313.1262, found 313.1257.

데이터(syn): 1H NMR δ 1.16 (s, 3H), 2.80 (br d, J = 3.3 Hz, 1H), 3.11 (d, J = 14.2 Hz, 1H), 3.56 (d, J = 14.2 Hz, 1H), 6.24 (dd, J = 17.4, 10.8 Hz, 1H) ppm.Data ( syn ): 1 H NMR δ 1.16 (s, 3H), 2.80 (br d, J = 3.3 Hz, 1H), 3.11 (d, J = 14.2 Hz, 1H), 3.56 (d, J = 14.2 Hz, 1H), 6.24 (dd, J = 17.4, 10.8 Hz, 1H) ppm.

실시 예 3-2. 4- 메틸 -1-(5- 벤젠설포닐 -4- 메틸 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 메틸 , R 2 = 수소, R 3 = 메틸인 경우. Example 3-2. 4-methyl-1- (5-benzenesulfonylamino-4-methyl-1,3-pentadienyl) benzene: R 1 = methyl, R 2 = a hydrogen, R 3 = methyl in the formula (I).

상기 실시 예 1-2와 같은 방법으로, 실시 예 3-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.35 g(1.05 mmol)을 벤젠 10 ㎖에 녹이고 파라-메틸벤즈알데하이드(화합물 F의 R3 = 메틸인 경우) 0.14 g(1.16 mmol)과 10-캠포설폰산 0.27 g(1.16 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 6시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 트랜스 구조의 이중결합을 함유하는 화학식 1로 표시되는 알릴릭 설폰 0.28 g(0.91 mmol)을 86%의 수율로 얻는다.In the same manner as in Example 1-2, 0.35 g (1.05 mmol) of the homoallylic alcohol of Formula 2, which is the result of Example 3-1, was dissolved in 10 ml of benzene, and para-methylbenzaldehyde (R 3 = In case of methyl) 0.14 g (1.16 mmol) and 0.27 g (1.16 mmol) of 10-camphorsulfonic acid were added, and then the reaction mixture was reacted at 100 ° C. for 6 hours, purified by chromatography on silica gel, and then trans 0.28 g (0.91 mmol) of allyl sulfone represented by the formula (1) containing a double bond of the structure is obtained in a yield of 86%.

데이터: 1H NMR δ 1.95 (s, 3H), 2.34 (s, 3H), 3.83 (s, 2H), 5.79 (d, J = 11.0 Hz, 1H), 6.35 (d, J = 15.6 Hz, 1H), 6.83 (dd, J = 11.0, 15.6 Hz, 1H), 7.12 (d, J = 8.1 Hz, 2H), 7.27 (d, J = 8.1 Hz, 2H), 7.51-7.66 (m, 3H), 7.84~7.87 (m, 2H) ppm; 13C NMR δ 17.6, 21.3, 66.7, 123.0, 123.4, 126.4, 128.5, 129.0, 129.4, 133.6, 134.2, 134.7, 137.9, 138.5 ppm; IR (KBr) 1509, 1446, 1314,1307, 1143 cm-1; HRMS (FAB+) cacld for C19H20O2S 312.1184, found 312.1194.Data: 1 H NMR δ 1.95 (s, 3H), 2.34 (s, 3H), 3.83 (s, 2H), 5.79 (d, J = 11.0 Hz, 1H), 6.35 (d, J = 15.6 Hz, 1H) , 6.83 (dd, J = 11.0, 15.6 Hz, 1H), 7.12 (d, J = 8.1 Hz, 2H), 7.27 (d, J = 8.1 Hz, 2H), 7.51-7.66 (m, 3H), 7.84- 7.87 (m, 2 H) ppm; 13 C NMR δ 17.6, 21.3, 66.7, 123.0, 123.4, 126.4, 128.5, 129.0, 129.4, 133.6, 134.2, 134.7, 137.9, 138.5 ppm; IR (KBr) 1509, 1446, 1314, 1307, 1143 cm −1 ; HRMS (FAB + ) cacld for C 19 H 20 O 2 S 312.1184, found 312.1194.

실시 예 4-1. 2- 벤젠설포닐메틸 -1-(4- 클로로페닐 )-2- 메틸 -3- 부텐 -1-올: 화학식 2의 R 1 = 메틸 , R 2 = 수소, R 3 = 염소인 경우. Example 4-1. 2- benzenesulfonylmethyl- 1- (4 -chlorophenyl ) -2- methyl- 3- butene -1-ol: where R 1 = methyl , R 2 = hydrogen, R 3 = chlorine of formula 2 :.

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-클로로-2-메틸-2-부텐(화합물 E의 R1 = 메틸, R2 = 수소, X = 염소인 경우) 0.39 g(1.60 mmol)을 THF 2 ㎖에 녹인 용액에 파라-클로로벤즈알데하이드(화합물 F의 R3 = 염소인 경우) 0.19 g(1.34 mmol), 인듐 0.17 g(1.47 mmol), 그리고 물 8 ㎖를 첨가한 다음 100 ℃로 3 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 0.46 g(1.31 mmol, anti:syn = 13:1) 을 98%의 수율로 얻는다. In the same manner as in Example 1-1, when 1-benzenesulfonyl-4-chloro-2-methyl-2-butene having a trans structure (R 1 = methyl, R 2 = hydrogen, X = chlorine of Compound E) ) 0.19 g (1.34 mmol) of para-chlorobenzaldehyde (if R 3 = chlorine of Compound F), 0.17 g (1.47 mmol) of indium, and 8 mL of water in a solution of 0.39 g (1.60 mmol) in 2 mL of THF. After the reaction was carried out at 100 ° C. for 3 hours, the mixture was purified by silica gel chromatography to obtain 0.46 g (1.31 mmol, anti : syn = 13: 1) of homoallylic alcohol represented by Chemical Formula 2 in 98% yield. Get into.

데이터(anti): 1H NMR δ 1.28 (s, 3H), 3.02 (br d, J = 3.8 Hz, 1H), 3.08 (d, J = 13.9 Hz, 1H), 3.54 (d, J = 13.9 Hz, 1H), 4.88 (d, J = 17.4 Hz, 1H), 5.06 (br d, J = 2.8 Hz, 1H), 5.09 (d, J = 10.8 Hz, 1H), 5.92 (dd, J = 17.4, 10.8 Hz, 1H), 7.21~7.28 (m, 4H), 7.53~7.68 (m, 3H), 7.89-7.93 (m, 2H) ppm; 13C NMR δ 19.8, 46.4, 62.5, 77.4, 116.1, 127.7, 127.7, 129.3, 129.4, 133.5, 133.7, 138.1, 139.4, 141.1 ppm; IR (KBr) 3503, 1447, 1306, 1148 cm-1; HRMS (FAB+) cacld for C18H18O2ClS (C18H19O3ClS - OH) 333.0716, found 333.0723.Data ( anti ): 1 H NMR δ 1.28 (s, 3H), 3.02 (br d, J = 3.8 Hz, 1H), 3.08 (d, J = 13.9 Hz, 1H), 3.54 (d, J = 13.9 Hz, 1H), 4.88 (d, J = 17.4 Hz, 1H), 5.06 (br d, J = 2.8 Hz, 1H), 5.09 (d, J = 10.8 Hz, 1H), 5.92 (dd, J = 17.4, 10.8 Hz , 1H), 7.21-7.28 (m, 4H), 7.53-77.6 (m, 3H), 7.89-7.93 (m, 2H) ppm; 13 C NMR δ 19.8, 46.4, 62.5, 77.4, 116.1, 127.7, 127.7, 129.3, 129.4, 133.5, 133.7, 138.1, 139.4, 141.1 ppm; IR (KBr) 3503, 1447, 1306, 1148 cm −1 ; HRMS (FAB + ) cacld for C 18 H 18 O 2 ClS (C 18 H 19 O 3 ClS-OH) 333.0716, found 333.0723.

데이터(syn): 1H NMR δ 1.08 (s, 3H), 3.07 (d, J = 13.9 Hz, 1H), 3.18 (d, J = 4.4 Hz, 1H), 3.55 (d, J = 13.9 Hz, 1H), 5.10 (d, J = 10.8 Hz, 1H), 6.31 (dd, J = 17.5, 10.8 Hz, 1H) ppm.Data ( syn ): 1 H NMR δ 1.08 (s, 3H), 3.07 (d, J = 13.9 Hz, 1H), 3.18 (d, J = 4.4 Hz, 1H), 3.55 (d, J = 13.9 Hz, 1H ), 5.10 (d, J = 10.8 Hz, 1H), 6.31 (dd, J = 17.5, 10.8 Hz, 1H) ppm.

실시 예 4-2. 4- 클로로 -1-(5- 벤젠설포닐 -4- 메틸 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 메틸 , R 2 = 수소, R 3 = 염소인 경우. Example 4-2. 4-chloro-1- (5-benzenesulfonylamino-4-methyl-1,3-pentadienyl) benzene: R 1 = methyl, R 2 = a hydrogen, R 3 = chlorine in the formula (I).

상기 실시 예 1-2와 같은 방법으로, 실시 예 4-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.39 g(1.10 mmol)을 벤젠 10 ㎖에 녹이고 파라-클로로벤즈알데하이드(화합물 F의 R3 = 염소인 경우) 0.17 g(1.21 mmol)과 10-캠포설폰산 0.28 g(1.21 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 24시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 트랜스 구조의 이중결합을 함유하는 화학식 1로 표시되는 알릴릭 설폰 0.19 g(0.57 mmol)을 52%의 수율로 얻는다.In the same manner as in Example 1-2, 0.39 g (1.10 mmol) of the homoallylic alcohol of Chemical Formula 2, which is the result of Example 4-1, was dissolved in 10 ml of benzene, and para-chlorobenzaldehyde (R 3 = In the case of chlorine), 0.17 g (1.21 mmol) and 0.28 g (1.21 mmol) of 10-camphorsulfonic acid were added, and the reaction mixture was reacted at 100 ° C. for 24 hours, and then purified by chromatography using silica gel. 0.19 g (0.57 mmol) of allylic sulfone represented by the formula (1) containing a double bond of the structure is obtained in a yield of 52%.

데이터: 1H NMR δ 1.96 (s, 3H), 3.84 (s, 2H), 5.83 (d, J = 10.8 Hz, 1H), 6.34 (d, J = 15.6 Hz, 1H), 6.85 (dd, J = 15.6, 10.8 Hz, 1H), 7.25~7.32 (m, 4H), 7.52~7.67 (m, 3H), 7.85~7.88 (m, 2H) ppm; 13C NMR δ 17.7, 66.7, 124.4, 125.9, 127.7, 128.5, 128.8, 129.1, 132.8, 133.5, 133.7, 134.3, 135.5, 138.6 ppm; IR (KBr) 1490, 1447, 1307, 1145, 1087 cm-1; HRMS (FAB+) cacld for C18H17O2ClS 332.0638, found 332.0634.Data: 1 H NMR δ 1.96 (s, 3H), 3.84 (s, 2H), 5.83 (d, J = 10.8 Hz, 1H), 6.34 (d, J = 15.6 Hz, 1H), 6.85 (dd, J = 15.6, 10.8 Hz, 1H), 7.25-7.72 (m, 4H), 7.52-7.07 (m, 3H), 7.85-7.88 (m, 2H) ppm; 13 C NMR δ 17.7, 66.7, 124.4, 125.9, 127.7, 128.5, 128.8, 129.1, 132.8, 133.5, 133.7, 134.3, 135.5, 138.6 ppm; IR (KBr) 1490, 1447, 1307, 1145, 1087 cm −1 ; HRMS (FAB + ) cacld for C 18 H 17 O 2 ClS 332.0638, found 332.0634.

실시 예 5-1. 2- 벤젠설포닐메틸 -2- 메틸 -1-(4- 메틸설파닐페닐 )-3- 부텐 -1-올: 화학식 2의 R 1 = 메틸 , R 2 = 수소, R 3 = 메틸설파닐인 경우. Example 5-1. 2- benzenesulfonylmethyl- 2 - methyl - 1- (4 -methylsulfanylphenyl ) -3- butene -1-ol: R 1 = methyl , R 2 = hydrogen, R 3 = methylsulfanyl If .

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-클로로-2-메틸-2-부텐(화합물 E의 R1 = 메틸, R2 = 수소, X = 염소인 경우) 5.25 g(21.44 mmol)을 THF 10 ㎖에 녹인 용액에 파라-메틸설파닐벤즈알데하이드(화합물 F의 R3 = 메틸설파닐인 경우) 3.58 g(23.58 mmol), 인듐 2.70 g(23.58 mmol), 그리고 물 40 ㎖를 첨가한 다음 100 ℃로 3.5 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 7.00 g(19.31 mmol, anti:syn = 13:1)을 90%의 수율로 얻는다. In the same manner as in Example 1-1, when 1-benzenesulfonyl-4-chloro-2-methyl-2-butene having a trans structure (R 1 = methyl, R 2 = hydrogen, X = chlorine of Compound E) ) 3.58 g (23.58 mmol) of para-methylsulfanylbenzaldehyde (if R 3 = methylsulfanyl of Compound F) in a solution of 5.25 g (21.44 mmol) in 10 mL of THF, 2.70 g (23.58 mmol) of indium, 40 ml of water was added thereto, followed by reaction at 100 ° C. for 3.5 hours, followed by purification by silica gel chromatography. Homoallylic alcohol represented by Chemical Formula 7.00 7.00 g (19.31 mmol, anti : syn = 13: 1) in 90% yield.

데이터(anti): 1H NMR δ 1.26 (s, 3H), 2.45 (s, 3H), 3.01 (br s, 1H), 3.14 (A of ABq, J AB = 14.1 Hz, 1H), 3.51 (B of ABq, J AB = 14.1 Hz, 1H), 4.89 (d, J = 17.5 Hz, 1H), 4.91 (br s, 1H), 5.08 (d, J = 10.9 Hz, 1H), 5.90 (dd, J = 17.5, 10.9 Hz, 1H), 7.12~7.22 (m, 4H), 7.50~7.66 (m, 3H), 7.85~7.92 (m, 2H) ppm; 13C NMR δ 15.6, 19.6, 46.2, 62.5, 78.1, 115.9, 125.5, 127.7, 128.5, 129.2, 133.6, 136.5, 137.9, 139.7, 141.2 ppm; IR (KBr) 3502, 1598, 1447, 1305, 1147 cm-1; HRMS (CI+) calcd for C19H21O3S2 361.0932, found 361.0936. Data ( anti ): 1 H NMR δ 1.26 (s, 3H), 2.45 (s, 3H), 3.01 (br s, 1H), 3.14 (A of ABq, J AB = 14.1 Hz, 1H), 3.51 (B of ABq, J AB = 14.1 Hz, 1H), 4.89 (d, J = 17.5 Hz, 1H), 4.91 (br s, 1H), 5.08 (d, J = 10.9 Hz, 1H), 5.90 (dd, J = 17.5 , 10.9 Hz, 1H), 7.12-7.22 (m, 4H), 7.50-7.72 (m, 3H), 7.85-7.92 (m, 2H) ppm; 13 C NMR δ 15.6, 19.6, 46.2, 62.5, 78.1, 115.9, 125.5, 127.7, 128.5, 129.2, 133.6, 136.5, 137.9, 139.7, 141.2 ppm; IR (KBr) 3502, 1598, 1447, 1305, 1147 cm −1 ; HRMS (CI + ) calcd for C 19 H 21 O 3 S 2 361.0932, found 361.0936.

데이터(syn): 1H NMR δ 1.12 (s, 3H), 2.46 (s, 3H), 6.21 (dd, J = 17.4, 10.8 Hz, 1H) ppm.Data syn : 1 H NMR δ 1.12 (s, 3H), 2.46 (s, 3H), 6.21 (dd, J = 17.4, 10.8 Hz, 1H) ppm.

실시 예 5-2. 4- 메틸설파닐 -1-(5- 벤젠설포닐 -4- 메틸 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 메틸 , R 2 = 수소, R 3 = 메틸설파닐인 경우. Example 5-2. 4-methylsulfanyl-1- (5-benzenesulfonylamino-4-methyl-1,3-pentadienyl) benzene: In case of R 1 = methyl, R 2 = hydrogen, R = 3-methylsulfanyl of formula .

상기 실시 예 1-2와 같은 방법으로, 실시 예 5-1의 결과물인 화학식 2의 호모알릴릭 알콜 2.96 g(8.15 mmol)을 벤젠 20 ㎖에 녹이고 파라-메틸설파닐벤즈알데하이드(화합물 F의 R3 = 메틸설파닐인 경우) 1.40 g(8.97 mmol)과 10-캠포설폰산 2.10 g(8.97 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 4시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 트랜스 구조의 이중결합을 함유하는 화학식 1로 표시되는 알릴릭 설폰 2.34 g(6.79 mmol)을 83%의 수율로 얻 는다.In the same manner as in Example 1-2, 2.96 g (8.15 mmol) of the homoallylic alcohol of Formula 2, which is the result of Example 5-1, was dissolved in 20 ml of benzene, and para-methylsulfanylbenzaldehyde (R of Compound F 3 = in case of methylsulfanyl) 1.40 g (8.97 mmol) and 2.10 g (8.97 mmol) of 10-camposulfonic acid were added, and then the reaction mixture was reacted at 100 ° C. for 4 hours, followed by chromatography using silica gel. Purification of the compound to obtain 2.34 g (6.79 mmol) of allyl sulfone represented by the formula (1) containing a double bond of the trans structure in 83% yield.

데이터: 1H NMR δ 1.95 (s, 3H), 2.48 (s, 3H), 3.83 (s, 2H), 5.81 (d, J = 10.9 Hz, 1H), 6.34 (d, J = 15.4 Hz, 1H), 6.84 (dd, J = 15.4, 10.9 Hz, 1H), 7.17~7.32 (m, 4H), 7.51~7.67 (m, 3H), 7.85~7.89 (m, 2H) ppm; 13C NMR δ 15.7, 17.7, 66.7, 123.3, 124.9, 126.5, 126.9, 128.5, 129.0, 133.6, 133.6, 133.9, 134.6, 138.4, 138.5 ppm; IR (KBr) 1588, 1489, 1446, 1307, 1149 cm-1; HRMS (FAB+) cacld for C19H21O2S2 345.0983, found 345.0981.Data: 1 H NMR δ 1.95 (s, 3H), 2.48 (s, 3H), 3.83 (s, 2H), 5.81 (d, J = 10.9 Hz, 1H), 6.34 (d, J = 15.4 Hz, 1H) , 6.84 (dd, J = 15.4, 10.9 Hz, 1H), 7.17-7.73 (m, 4H), 7.51-7.67 (m, 3H), 7.85-7.89 (m, 2H) ppm; 13 C NMR δ 15.7, 17.7, 66.7, 123.3, 124.9, 126.5, 126.9, 128.5, 129.0, 133.6, 133.6, 133.9, 134.6, 138.4, 138.5 ppm; IR (KBr) 1588, 1489, 1446, 1307, 1149 cm −1 ; HRMS (FAB + ) cacld for C 19 H 21 O 2 S 2 345.0983, found 345.0981.

실시 예 6-1. 2- 벤젠설포닐메틸 -1- 페닐 -3- 부텐 -1-올: 화학식 2의 R 1 = 수소, R 2 = 수소, R 3 = 수소인 경우. Example 6-1. 2- benzenesulfonylmethyl- 1- phenyl- 3- butene -1-ol: when R 1 = hydrogen, R 2 = hydrogen, R 3 = hydrogen in formula 2 .

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-브로모-2-부텐(화합물 E의 R1 = 수소, R2 = 수소, X = 브롬인 경우) 0.44 g(1.58 mmol)을 THF 4 ㎖에 녹인 용액에 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.18 g(1.74 mmol), 인듐 0.20 g(1.74 mmol), 그리고 물 16 ㎖를 첨가한 다음 100 ℃로 1.5 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 0.41 g(1.37 mmol, anti:syn = 2:1)을 86%의 수율로 얻는다. 0.44 g of 1-benzenesulfonyl-4-bromo-2-butene having a trans structure in case of R 1 = hydrogen, R 2 = hydrogen, X = bromine of a trans structure in the same manner as in Example 1-1 (1.58 mmol) in 4 ml of THF was added 0.18 g (1.74 mmol) of benzaldehyde (if R 3 = hydrogen of Compound F), 0.20 g (1.74 mmol) of indium, and 16 ml of water, followed by 100 ° C. After reacting for 1.5 hours, the reaction mixture was purified by silica gel chromatography to obtain 0.41 g (1.37 mmol, anti : syn = 2: 1) of homoallylic alcohol represented by Chemical Formula 2 in a yield of 86%.

데이타(anti): 1H NMR δ 2.84-2.97 (m, 2H), 3.07 (d of ABq, J AB = 14.2, J d = 8.0 Hz, 1H), 3.40 (d of ABq, J AB = 14.2, J d = 4.9 Hz, 1H), 4.80 (dd, J = 3.8, 3.8 Hz, 1H), 4.90 (d, J = 17.2 Hz, 1H), 5.02 (d, J = 10.1 Hz, 1H), 5.51 (ddd, J = 17.2, 10.1, 8.9 Hz, 1H), 7.14~7.30 (m, 5H), 7.41~7.63 (m, 3H), 7.70~7.82 (m, 2H) ppm; 13C NMR δ 46.2, 56.8, 74.7, 119.6, 126.3, 128.0, 128.4, 129.1, 129.2, 133.7, 134.7, 135.6, 156.5 ppm; IR (KBr) 3501, 1448, 1305, 1145 cm-1; HRMS (FAB+) cacld for C17H17O2S (C17H18O3S - OH) 285.0949, found 285.0948. Anti : 1 H NMR δ 2.84-2.97 (m, 2H), 3.07 (d of ABq, J AB = 14.2, J d = 8.0 Hz, 1H), 3.40 (d of ABq, J AB = 14.2, J d = 4.9 Hz, 1H), 4.80 (dd, J = 3.8, 3.8 Hz, 1H), 4.90 (d, J = 17.2 Hz, 1H), 5.02 (d, J = 10.1 Hz, 1H), 5.51 (ddd, J = 17.2, 10.1, 8.9 Hz, 1H), 7.14-7.30 (m, 5H), 7.41-7.63 (m, 3H), 7.70-7.82 (m, 2H) ppm; 13 C NMR δ 46.2, 56.8, 74.7, 119.6, 126.3, 128.0, 128.4, 129.1, 129.2, 133.7, 134.7, 135.6, 156.5 ppm; IR (KBr) 3501, 1448, 1305, 1145 cm −1 ; HRMS (FAB + ) cacld for C 17 H 17 O 2 S (C 17 H 18 O 3 S -OH) 285.0949, found 285.0948.

데이타(syn): 1H NMR δ 3.20 (d of ABq, J AB = 14.4, J d = 9.2 Hz, 1H), 3.38 (d of ABq, J AB = 14.4, J d = 3.2 Hz, 1H), 4.63 (dd, J = 5.1, 4.2 Hz, 1H), 4.95 (d, J = 17.2 Hz, 1H), 5.60 (ddd, J = 17.2, 10.2, 8.4 Hz, 1H) ppm.Data ( syn ): 1 H NMR δ 3.20 (d of ABq, J AB = 14.4, J d = 9.2 Hz, 1H), 3.38 (d of ABq, J AB = 14.4, J d = 3.2 Hz, 1H), 4.63 (dd, J = 5.1, 4.2 Hz, 1H), 4.95 (d, J = 17.2 Hz, 1H), 5.60 (ddd, J = 17.2, 10.2, 8.4 Hz, 1H) ppm.

실시 예 6-2. (5- 벤젠설포닐 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 수소, R 2 = 수소, R 3 = 수소인 경우. Example 6-2. (5- Benzenesulfonyl -1,3- pentadienyl ) benzene: when R 1 of formula 1 is hydrogen, R 2 is hydrogen, R 3 is hydrogen .

상기 실시 예 1-2와 같은 방법으로, 실시 예 6-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.51 g(1.68 mmol, anti:syn = 2:1)을 벤젠 15 ㎖에 녹이고 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.20 g(1.85 mmol)과 10-캠포설폰산 0.43 g(1.85 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 5시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 화학식 1로 표시되는 알릴릭 설폰 0.33 g(1.15 mmol, E:Z = 2:1 at C-2)을 68%의 수율로 얻는다.In the same manner as in Example 1-2, 0.51 g (1.68 mmol, anti : syn = 2: 1) of the homoallylic alcohol of Chemical Formula 2, which is the result of Example 6-1, was dissolved in 15 ml of benzene and benzaldehyde (compound). F, R 3 = a hydrogen) 0.20 g (1.85 mmol) and 10-camphorsulfonic acid plus 0.43 g (1.85 mmol) after which the reaction for 5 hours the reaction mixture to 100 ℃, of chromatography with silica gel Purification by the method to obtain 0.33 g (1.15 mmol, E : Z = 2: 1 at C-2) of allyl sulfone represented by the formula (1) in a yield of 68%.

데이터(all-E): 1H NMR δ 3.89 (d, J = 7.7 Hz, 2H), 5.69 (dt, J d = 15.2, J t = 7.7 Hz, 1H), 6.19 (dd, J = 15.2, 10.5 Hz, 1H), 6.48 (d, J = 15.8 Hz, 1H), 6.72 (dd, J = 15.8, 10.5 Hz, 1H), 7.25~7.34 (m, 5H), 7.48~7.68 (m, 3H), 7.87~7.89 (m, 2H) ppm; 13C NMR δ 60.4, 118.2, 126.5, 127.1, 128.1, 128.4, 128.6, 129.0, 133.7, 134.8, 136.5, 138.4, 139.4 ppm; IR (KBr) 1448, 1307, 1145 cm-1; HRMS (FAB+) cacld for C17H16O2S 284.0871, found 284.0879.Data (all- E ): 1 H NMR δ 3.89 (d, J = 7.7 Hz, 2H), 5.69 (dt, J d = 15.2, J t = 7.7 Hz, 1H), 6.19 (dd, J = 15.2, 10.5 Hz, 1H), 6.48 (d, J = 15.8 Hz, 1H), 6.72 (dd, J = 15.8, 10.5 Hz, 1H ), 7.25-7.74 (m, 5H), 7.48-7.68 (m, 3H), 7.87-7.89 (m, 2H) ppm; 13 C NMR δ 60.4, 118.2, 126.5, 127.1, 128.1, 128.4, 128.6, 129.0, 133.7, 134.8, 136.5, 138.4, 139.4 ppm; IR (KBr) 1448, 1307, 1145 cm −1 ; HRMS (FAB + ) cacld for C 17 H 16 O 2 S 284.0871, found 284.0879.

데이터(2-Z): 1H NMR δ 4.06 (d, J = 7.5 Hz, 2H), 5.42 (dt, J d = 10.3, J t = 7.5 Hz, 1H), 6.37 (dd, J = 10.5, 10.3 Hz, 1H), 6.30~6.58 (m, 2H), 7.20~7.65 (m, 8H), 7.83~7.95 (m, 2H) ppm.Data (2- Z ): 1 H NMR δ 4.06 (d, J = 7.5 Hz, 2H), 5.42 (dt, J d = 10.3, J t = 7.5 Hz, 1H), 6.37 (dd, J = 10.5, 10.3 Hz, 1H), 6.30-6.58 (m, 2H), 7.20-7.75 (m, 8H), 7.83-7.95 (m, 2H) ppm.

실시 예 7-1. 2- 벤젠설포닐메틸 -1,2- 디페닐 -3- 부텐 -1-올: 화학식 2의 R 1 = 페닐, R 2 = 수소, R 3 = 수소인 경우. Example 7-1. 2- benzenesulfonylmethyl- 1,2 -diphenyl- 3- butene -1-ol: where R 1 = phenyl , R 2 = hydrogen, R 3 = hydrogen in formula 2 .

상기 실시 예 1-1과 같은 방법으로, 씨스(cis) 구조의 1-벤젠설포닐-4-클로로-2-페닐-2-부텐(화합물 E의 R1 = 페닐, R2 = 수소, X = 염소인 경우) 0.39 g(1.26 mmol)을 THF 2 ㎖에 녹인 용액에 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.16 g(1.51 mmol), 인듐 0.16 g(1.39 mmol), 그리고 물 8 ㎖를 첨가한 다음 100 ℃로 2.5 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 0.21 g(0.57 mmol, anti:syn = 1:13)을 45%의 수율로 얻는다.In the same manner as in Example 1-1, 1-benzenesulfonyl-4-chloro-2-phenyl-2-butene having a cis structure (R 1 = Phenyl, R 2 = H, X = Chlorine) 0.16 g (1.51 mmol) benzaldehyde (if R 3 = hydrogen of Compound F), 0.16 g (1.39 mmol), and 8 mL water in a solution of 0.39 g (1.26 mmol) in 2 mL THF. After the reaction was carried out at 100 ℃ for 2.5 hours, and purified by silica gel chromatography method 0.21 g (0.57 mmol, anti : syn = 1: 13) of the homoallylic alcohol represented by the formula (2) 45% yield Get into.

데이터(syn): 1H NMR δ 2.70 (br s, 1H), 3.57 (ABq, J = 14.7 Hz, 1H), 3.86 (ABq, J = 14.7 Hz, 1H), 5.08 (d, J = 17.8 Hz, 1H), 5.42 (d, J = 11.2 Hz, 1H), 5.87 (s, 1H), 6.32 (dd, J = 17.8, 11.2 Hz, 1H), 7.12~7.35 (m, 10H), 7.36~7.44 (m, 2H), 7.48~7.63 (m, 3H) ppm; 13C NMR δ 53.5, 62.5, 76.3, 127.3, 127.4, 127.6, 128.0, 128.5, 128.7, 128.9, 130.1, 133.0, 133.6, 138.4, 138.6, 139.5, 141.4 ppm; IR (KBr) 3503, 1447, 1307, 1149 cm-1; HRMS (FAB+) cacld for C23H21O2S (C23H22O3S - OH) 361.1262, found 361.1271. Data ( syn ): 1 H NMR δ 2.70 (br s, 1H), 3.57 (ABq, J = 14.7 Hz, 1H), 3.86 (ABq, J = 14.7 Hz, 1H), 5.08 (d, J = 17.8 Hz, 1H), 5.42 (d, J = 11.2 Hz, 1H), 5.87 (s, 1H), 6.32 (dd, J = 17.8, 11.2 Hz, 1H), 7.12-7.35 (m, 10H), 7.36-7.44 (m , 2H), 7.48-7.63 (m, 3H) ppm; 13 C NMR δ 53.5, 62.5, 76.3, 127.3, 127.4, 127.6, 128.0, 128.5, 128.7, 128.9, 130.1, 133.0, 133.6, 138.4, 138.6, 139.5, 141.4 ppm; IR (KBr) 3503, 1447, 1307, 1149 cm −1 ; HRMS (FAB + ) cacld for C 23 H 21 O 2 S (C 23 H 22 O 3 S -OH) 361.1262, found 361.1271.

데이터(anti): 1H NMR δ 6.18 (dd, J = 17.8, 11.2 Hz, 1H) ppm.Data ( anti ): 1 H NMR δ 6.18 (dd, J = 17.8, 11.2 Hz, 1H) ppm.

실시 예 7-2. (5- 벤젠설포닐 -4- 페닐 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 페닐, R 2 = 수소, R 3 = 수소인 경우. Example 7-2. (5- Benzenesulfonyl - 4- phenyl -1,3- pentadienyl ) benzene: when R 1 of formula 1 = phenyl , R 2 = hydrogen, R 3 = hydrogen .

상기 실시 예 1-2와 같은 방법으로, 실시 예 7-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.13 g(0.34 mmol, anti:syn = 1:13)을 벤젠 10 ㎖에 녹이고 벤즈알 데하이드(화합물 F의 R3 = 수소인 경우) 0.035 g(0.34 mmol)과 10-캠포설폰산 0.086 g(0.37 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 4시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 2-번 탄소에 씨스 구조의 이중결합을 함유하는 화학식 1로 표시되는 알릴릭 설폰 0.073 g(0.20 mmol)을 60%의 수율로 얻는다.In the same manner as in Example 1-2, 0.13 g (0.34 mmol, anti : syn = 1:13) of the homoallylic alcohol of Chemical Formula 2, which is a result of Example 7-1, was dissolved in 10 ml of benzene and benzaldehyde. (compound F of R 3 = a hydrogen) 0.035 g (0.34 mmol) and 10-camphor sulfonic acid 0.086 g (0.37 mmol) of adding the reaction mixture after reacting for 4 hours in 100 ℃, chromatography using silica gel Purification by chromatography yields 0.073 g (0.20 mmol) of allylic sulfone represented by the formula (1) containing a double bond of a seed structure on carbon No. 2 in a yield of 60%.

데이터(2-Z): 1H NMR δ 4.56 (s, 2H), 6.61 (d, J = 14.8 Hz, 1H), 6.71 (d, J = 11.0 Hz, 1H), 6.82 (dd, J = 14.8, 11.0 Hz, 1H), 7.15~7.41 (m, 13H), 7.75~7.81 (m, 2H) ppm; 13C NMR δ 58.0, 124.0, 126.2, 126.8, 127.6, 127.7, 128.2, 128.4, 128.5, 128.6, 128.8, 133.6, 134.9, 136.6, 136.7, 138.5, 140.2 ppm; IR (KBr) 1541, 1507, 1457, 1320, 1150 cm-1; HRMS (FAB+) cacld for C23H20O2S 360.1184, found 360.1190.Data (2- Z ): 1 H NMR δ 4.56 (s, 2H), 6.61 (d, J = 14.8 Hz, 1H), 6.71 (d, J = 11.0 Hz, 1H), 6.82 (dd, J = 14.8, 11.0 Hz, 1H), 7.15-7.41 (m, 13H), 7.75-7.81 (m, 2H) ppm; 13 C NMR δ 58.0, 124.0, 126.2, 126.8, 127.6, 127.7, 128.2, 128.4, 128.5, 128.6, 128.8, 133.6, 134.9, 136.6, 136.7, 138.5, 140.2 ppm; IR (KBr) 1541, 1507, 1457, 1320, 1150 cm −1 ; HRMS (FAB + ) cacld for C 23 H 20 O 2 S 360.1184, found 360.1190.

실시 예 8-1. 2- 벤젠설포닐메틸 -3- 메틸 -1- 페닐 -3- 부텐 -1-올: 화학식 2의 R 1 = 수소, R 2 = 메틸 , R 3 = 수소인 경우. Example 8-1. 2- benzenesulfonylmethyl- 3 - methyl - 1- phenyl- 3- butene -1-ol: when R 1 = hydrogen, R 2 = methyl , R 3 = hydrogen in formula 2 .

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-클로로-3-메틸-2-부텐(화합물 E의 R1 = 수소, R2 = 메틸, X = 염소인 경우) 2.06 g(8.41 mmol)을 THF 4 ㎖에 녹인 용액에 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 1.07 g(10.10 mmol), 인듐 1.06 g(9.25 mmol), 그리고 물 16 ㎖를 첨가한 다음 100 ℃로 3 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 2.40 g(7.57 mmol, anti:syn = 2:1)을 90%의 수율로 얻는다. In the same manner as in Example 1-1, when 1-benzenesulfonyl-4-chloro-3-methyl-2-butene having a trans structure (R 1 = hydrogen, R 2 = methyl, X = chlorine of Compound E) ) 2.07 g (8.41 mmol) in 4 ml of THF was added 1.07 g (10.10 mmol) of benzaldehyde (if R 3 = hydrogen of Compound F), 1.06 g (9.25 mmol) of indium, and 16 ml of water. Next, the reaction was carried out at 100 ° C. for 3 hours, and purified by silica gel chromatography to obtain 2.40 g (7.57 mmol, anti : syn = 2: 1) of homoallylic alcohol represented by Chemical Formula 2 in a yield of 90%.

데이터(anti): 1H NMR δ 1.59 (s, 3H), 2.17 (br s, 1H), 2.86~2.97 (m, 1H), 3.42 (d of ABq, J AB = 14.5, J d = 9.7 Hz, 1H), 3.59 (d of ABq, J AB = 14.5, J d = 2.8 Hz, 1H), 4.59 (d, J = 6.6 Hz, 1H), 4.69 (s, 1H), 4.81 (s, 1H), 7.18~7.35 (m, 5H), 7.47~7.56 (m, 2H), 7.58~7.67 (m, 1H), 7.75~7.84 (m, 2H) ppm; 13C NMR δ 20.0, 48.8, 55.5, 74.0, 114.9, 126.6, 128.0, 128.0, 128.4, 128.6, 129.0, 133.5, 139.1, 141.7 ppm; IR (KBr) 3491, 1458, 1305, 1137 cm-1; HRMS (CI+) cacld for C18H19O2S (C18H20O3S - OH) 299.1106, found 299.1103.Data ( anti ): 1 H NMR δ 1.59 (s, 3H), 2.17 (br s, 1H), 2.86-2.97 (m, 1H), 3.42 (d of ABq, J AB = 14.5, J d = 9.7 Hz, 1H), 3.59 (d of ABq, J AB = 14.5, J d = 2.8 Hz, 1H), 4.59 (d, J = 6.6 Hz, 1H), 4.69 (s, 1H), 4.81 (s, 1H), 7.18 ~ 7.35 (m, 5H), 7.47-7.56 (m, 2H), 7.58-7.67 (m, 1H), 7.75-7.84 (m, 2H) ppm; 13 C NMR δ 20.0, 48.8, 55.5, 74.0, 114.9, 126.6, 128.0, 128.0, 128.4, 128.6, 129.0, 133.5, 139.1, 141.7 ppm; IR (KBr) 3491, 1458, 1305, 1137 cm −1 ; HRMS (CI + ) cacld for C 18 H 19 O 2 S (C 18 H 20 O 3 S -OH) 299.1106, found 299.1103.

데이터(syn): 1H NMR δ 1.60 (s, 3H), 2.26 (br s, 1H), 3.12 (d of ABq, J AB = 14.5, J d = 4.0 Hz, 1H), 3.24 (d of ABq, J AB = 14.5, J d = 9.5 Hz, 1H), 4.62 (d, J = 10.5 Hz, 1H), 4.86 (s, 1H), 5.01 (s, 1H) ppm.Data ( syn ): 1 H NMR δ 1.60 (s, 3H), 2.26 (br s, 1H), 3.12 (d of ABq, J AB = 14.5, J d = 4.0 Hz, 1H), 3.24 (d of ABq, J AB = 14.5, J d = 9.5 Hz, 1H), 4.62 (d, J = 10.5 Hz, 1H), 4.86 (s, 1H), 5.01 (s, 1H) ppm.

실시 예 8-2. (5- 벤젠설포닐 -3- 메틸 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 수소, R 2 = 메틸 , R 3 = 수소인 경우. Example 8-2. (5-benzenesulfonyl-3-methyl-1,3-pentadienyl) benzene: R = 1 in formula (1) a hydrogen, R 2 = methyl, the R 3 = hydrogen.

상기 실시 예 1-2와 같은 방법으로, 실시 예 8-1의 결과물인 화학식 2의 호 모알릴릭 알콜 0.24 g(0.77 mmol, anti:syn = 2:1)과 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.09 g(0.84 mmol)을 3 M HCl 수용액 20 ㎖에 더한 다음, 반응 혼합물을 100 ℃로 5.5 시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 화학식 1로 표시되는 알릴릭 설폰 0.17 g(0.57 mmol, E:Z = 2:1 at C-2)을 74%의 수율로 얻는다.In the same manner as in Example 1-2, 0.24 g (0.77 mmol, anti : syn = 2: 1) of homomolylic alcohol of Chemical Formula 2, which is a result of Example 8-1, and benzaldehyde (R 3 of Compound F) = Hydrogen) 0.09 g (0.84 mmol) was added to 20 ml of 3 M HCl aqueous solution, and then the reaction mixture was reacted at 100 ° C. for 5.5 hours, and then purified by chromatography using silica gel, which is represented by Formula 1. 0.17 g (0.57 mmol, E : Z = 2: 1 at C-2) of allyl sulfone is obtained in a yield of 74%.

데이터(all-E): 1H NMR δ 1.53 (s, 3H), 3.99 (d, J = 8.3 Hz, 2H), 5.57 (t, J = 8.3 Hz, 1H), 6.51 (d, J = 16.0 Hz, 1H), 6.77 (d, J = 16.0 Hz, 1H), 7.20~7.71 (m, 8H), 7.83~7.92 (m, 2H) ppm; 13C NMR d 12.3, 56.5, 116.8, 126.5, 127.8, 128.4, 128.6, 129.1, 129.6, 131.6, 133.7, 136.8, 138.5, 142.3 ppm; IR (KBr) 1447, 1306, 1151, 1090 cm-1; HRMS (FAB+) cacld for C18H18O2S 298.1027, found 298.1021.Data (all- E ): 1 H NMR δ 1.53 (s, 3H), 3.99 (d, J = 8.3 Hz, 2H), 5.57 (t, J = 8.3 Hz, 1H), 6.51 (d, J = 16.0 Hz , 1H), 6.77 (d, J = 16.0 Hz, 1H), 7.20-7.71 (m, 8H), 7.83-7.82 (m, 2H) ppm; 13 C NMR d 12.3, 56.5, 116.8, 126.5, 127.8, 128.4, 128.6, 129.1, 129.6, 131.6, 133.7, 136.8, 138.5, 142.3 ppm; IR (KBr) 1447, 1306, 1151, 1090 cm -1 ; HRMS (FAB + ) cacld for C 18 H 18 O 2 S 298.1027, found 298.1021.

데이터(2-Z): 1H NMR δ 1.95 (s, 3H), 4.04 (d, J = 8.3 Hz, 2H), 5.41 (t, J = 8.3 Hz, 1H), 6.51 (A of ABq, J = 16.0 Hz, 1H), 6.58 (B of ABq, J = 16.0 Hz, 1H), 7.20~7.73 (m, 8H), 7.83~7.91 (m, 2H) ppm; 13C NMR δ 20.6, 55.5, 114.7, 126.7, 128.0, 128.3, 128.5, 128.9, 129.6, 131.7, 133.5, 136.7, 139.2, 142.3 ppm.Data (2- Z ): 1 H NMR δ 1.95 (s, 3H), 4.04 (d, J = 8.3 Hz, 2H), 5.41 (t, J = 8.3 Hz, 1H), 6.51 (A of ABq, J = 16.0 Hz, 1H), 6.58 (B of ABq, J = 16.0 Hz, 1H), 7.20-7.73 (m, 8H), 7.83-7.91 (m, 2H) ppm; 13 C NMR δ 20.6, 55.5, 114.7, 126.7, 128.0, 128.3, 128.5, 128.9, 129.6, 131.7, 133.5, 136.7, 139.2, 142.3 ppm.

실시 예 9-1. 2- 벤젠설포닐메틸 -1,3- 디페닐 -3- 부텐 -1-올: 화학식 2의 R 1 = 수소, R 2 = 페닐 , R 3 = 수소인 경우. Example 9-1. 2- benzenesulfonylmethyl- 1,3 -diphenyl- 3- butene -1-ol: when R 1 in formula 2 = hydrogen, R 2 = phenyl , R 3 = hydrogen .

상기 실시 예 1-1과 같은 방법으로, 트랜스 구조의 1-벤젠설포닐-4-클로로-3-페닐-2-부텐(화합물 E의 R1 = 수소, R2 = 페닐, X = 염소인 경우) 0.47 g(1.54 mmol)을 THF 2 ㎖에 녹인 용액에 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.20 g(1.85 mmol), 인듐 0.19 g(1.69 mmol), 그리고 물 8 ㎖를 첨가한 다음 100 ℃로 3 시간 동안 반응시킨 뒤, 실리카겔 크로마토 그라피의 방법으로 정제하여 화학식 2로 표시되는 호모알릴릭 알콜 0.42 g(1.11 mmol, anti:syn = 1:4)을 72%의 수율로 얻는다. In the same manner as in Example 1-1, when 1-benzenesulfonyl-4-chloro-3-phenyl-2-butene having a trans structure (R 1 = hydrogen, R 2 = phenyl, X = chlorine of Compound E) ) 0.20 g (1.85 mmol) of benzaldehyde (if R 3 = hydrogen of Compound F), 0.19 g (1.69 mmol), and 8 ml of water were added to a solution of 0.47 g (1.54 mmol) in 2 ml of THF. After reaction for 3 hours at 100 ℃, purified by silica gel chromatography to obtain 0.42 g (1.11 mmol, anti : syn = 1: 4) of the homoallylic alcohol represented by the formula (2) in a yield of 72%.

데이터(syn): 1H NMR δ 2.31 (br s, 1H), 3.54 (ABq, J = 13.7 Hz, 1H), 3.62 (d of ABq, J AB = 13.7, J d = 10.3 Hz, 1H), 3.50~3.65 (m, 1H), 4.67 (d, J = 4.2 Hz, 1H), 5.08 (s, 1H), 5.34 (s, 1H), 7.13~7.30 (m, 10H), 7.40~7.50 (m, 2H), 7.55~7.64 (m, 1H), 7.70~7.80 (m, 2H) ppm; 13C NMR δ 46.9, 55.4, 74.6, 115.9, 126.1, 126.7, 127.6, 127.7, 127.9, 128.2, 128.3, 129.1, 133.5, 139.6, 140.9, 141.4, 146.1, 146.9 ppm; IR (KBr) 3497, 1447, 1306, 1139 cm-1; HRMS (CI+) cacld for C23H21O2S (C23H22O3S - OH) 361.1262, found 361.1264.Data ( syn ): 1 H NMR δ 2.31 (br s, 1H), 3.54 (ABq, J = 13.7 Hz, 1H), 3.62 (d of ABq, J AB = 13.7, J d = 10.3 Hz, 1H), 3.50 ~ 3.65 (m, 1H), 4.67 (d, J = 4.2 Hz, 1H), 5.08 (s, 1H), 5.34 (s, 1H), 7.13-7.30 (m, 10H), 7.40-7.50 (m, 2H ), 7.55-7.74 (m, 1H), 7.70-7.80 (m, 2H) ppm; 13 C NMR δ 46.9, 55.4, 74.6, 115.9, 126.1, 126.7, 127.6, 127.7, 127.9, 128.2, 128.3, 129.1, 133.5, 139.6, 140.9, 141.4, 146.1, 146.9 ppm; IR (KBr) 3497, 1447, 1306, 1139 cm −1 ; HRMS (CI + ) cacld for C 23 H 21 O 2 S (C 23 H 22 O 3 S -OH) 361.1262, found 361.1264.

데이터(anti): 1H NMR δ 2.60 (br s, 1H), 3.31 (d of ABq, J AB = 13.9, J d = 8.3 Hz, 1H), 3.49 (d of ABq, J AB = 13.9, J d = 4.6 Hz, 1H), 3.52~3.60 (m, 1H), 4.86 (d, J = 4.9 Hz, 1H), 5.00 (s, 1H), 5.32 (s, 1H) ppm.Data ( anti ): 1 H NMR δ 2.60 (br s, 1H), 3.31 (d of ABq, J AB = 13.9, J d = 8.3 Hz, 1H), 3.49 (d of ABq, J AB = 13.9, J d = 4.6 Hz, 1H), 3.52-3.60 (m, 1H), 4.86 (d, J = 4.9 Hz, 1H), 5.00 (s, 1H), 5.32 (s, 1H) ppm.

실시 예 9-2. (5- 벤젠설포닐 -3- 페닐 -1,3- 펜타디에닐 )벤젠: 화학식 1의 R 1 = 수소, R 2 = 페닐 , R 3 = 수소인 경우. Example 9-2. (5- Benzenesulfonyl - 3- phenyl -1,3- pentadienyl ) benzene: when R 1 in formula 1 = hydrogen, R 2 = phenyl , R 3 = hydrogen .

상기 실시 예 1-2와 같은 방법으로, 실시 예 9-1의 결과물인 화학식 2의 호모알릴릭 알콜 0.61 g(1.62 mmol, anti:syn = 1:4)을 벤젠 20 ㎖에 녹이고 벤즈알데하이드(화합물 F의 R3 = 수소인 경우) 0.19 g(1.79 mmol)과 10-캠포설폰산 0.42 g(1.79 mmol)을 더한 다음, 반응 혼합물을 100 ℃로 4시간 동안 반응시킨 뒤, 실리카겔을 이용한 크로마토그래피의 방법으로 정제하여 화학식 1로 표시되는 알릴릭 설폰 0.44 g(1.26 mmol, E:Z = 2:3 at C-2)을 77%의 수율로 얻는다.In the same manner as in Example 1-2, 0.61 g (1.62 mmol, anti : syn = 1: 4) of the homoallylic alcohol of Chemical Formula 2, which is the result of Example 9-1, was dissolved in 20 ml of benzene and benzaldehyde (compound). F, R 3 = a hydrogen) 0.19 g (after which 1.79 mmol) and 10-camphorsulfonic acid plus 0.42 g (1.79 mmol), and the reaction for 4 hours the reaction mixture to 100 ℃, of chromatography with silica gel Purification by the method to obtain 0.44 g (1.26 mmol, E : Z = 2: 3 at C-2) of allyl sulfone represented by Chemical Formula 1 in a yield of 77%.

데이터(2-Z): 1H NMR δ 4.19 (d, J = 8.4 Hz, 2H), 5.53 (t, J = 8.4 Hz, 1H), 6.23 (d, J = 16.0 Hz, 1H), 6.67 (d, J = 16.0 Hz, 1H), 7.15~7.67 (m, 13H), 7.88~7.95 (m, 2H) ppm; IR (KBr) 1558, 1507, 1447, 1325, 1151 cm-1; HRMS (FAB+) cacld for C23H21O3S 361.1262, found 361.1272.Data (2- Z ): 1 H NMR δ 4.19 (d, J = 8.4 Hz, 2H), 5.53 (t, J = 8.4 Hz, 1H), 6.23 (d, J = 16.0 Hz, 1H), 6.67 (d , J = 16.0 Hz, 1H), 7.15-7.67 (m, 13H), 7.88-7.95 (m, 2H) ppm; IR (KBr) 1558, 1507, 1447, 1325, 1151 cm −1 ; HRMS (FAB + ) cacld for C 23 H 21 O 3 S 361.1262, found 361.1272.

데이터(all-E): 1H NMR δ 3.76 (d, J = 8.1 Hz, 2H), 5.87 (t, J = 8.1 Hz, 1H), 5.99 (d, J = 15.9 Hz, 1H), 6.97 (d, J = 15.9 Hz, 1H), 7.15~7.67 (m, 13H), 7.73~7.78 (m, 2H) ppm.Data (all- E ): 1 H NMR δ 3.76 (d, J = 8.1 Hz, 2H), 5.87 (t, J = 8.1 Hz, 1H), 5.99 (d, J = 15.9 Hz, 1H), 6.97 (d , J = 15.9 Hz, 1H), 7.15-7.67 (m, 13H), 7.73-77.7 (m, 2H) ppm.

이상의 실시 예를 종합 정리하여 다음의 그림과 표에 요약하였다.The above embodiments are collectively summarized in the following figures and tables.

Figure 112006012413348-pat00008
Figure 112006012413348-pat00008

실시 예Example 화합물ECompound E 화합물FCompound F 화학식2Formula 2 화학식1Formula 1 R1 R 1 R2 R 2 XX R3 R 3 수율(%)yield(%) antianti :: synsyn 수율(%)yield(%) E:ZE: Z 1One MeMe HH ClCl HH 9898 13:113: 1 7070 EE 22 MeMe HH ClCl OMeOMe 8080 13:113: 1 8080 EE 33 MeMe HH ClCl MeMe 9090 13:113: 1 8686 EE 44 MeMe HH ClCl ClCl 9898 13:113: 1 5252 EE 55 MeMe HH ClCl SMeSMe 9090 13:113: 1 8383 EE 66 HH HH BrBr HH 8686 2:12: 1 6868 2:12: 1 77 PhPh HH ClCl HH 4545 1:131:13 6060 ZZ 88 HH MeMe ClCl HH 9090 2:12: 1 7474 2:12: 1 99 HH PhPh ClCl HH 7272 1:41: 4 7777 2:32: 3

이상에서 살펴본 바와 같이 본 발명에 따르면, 양끝에 벤젠고리를 함유하는 카로틴 화합물의 합성에 효율적으로 사용되는 화학식 1로 표시되는 신규의 알릴릭 설폰 화합물을 입체 선택적으로 합성할 수 있다. 벤젠고리를 함유하는 카로틴 화합물은 매우 우수한 항산화제 및 라디칼 제거제로 사용될 수 있고, 비교적 안정하며, 전기 화학적 특성을 지녀 산업적으로 응용가치가 높을 것으로 예상되는 중요한 화합물이다.As described above, according to the present invention, it is possible to stereoselectively synthesize a novel allylic sulfone compound represented by Chemical Formula 1, which is efficiently used for the synthesis of a carotene compound containing a benzene ring at both ends. Carotene compounds containing benzene rings are important compounds that can be used as very good antioxidants and radical scavengers, are relatively stable, have electrochemical properties and are expected to be of high industrial value.

Claims (7)

화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰.Allyl sulfone containing a benzene ring represented by the formula (1).
Figure 112006012413348-pat00009
Figure 112006012413348-pat00009
 상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되며, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택된다. 단, R1과 R3가 모두 H 이고, R2가 H 이거나 Me인 경우는 제외한다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me, Ph, and R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl. Provided that both R 1 and R 3 are H and R 2 is H or Me. 화학식 2로 표시되는 호모알릴릭 설폰기를 함유하는 호모알릴릭 알콜.A homoallylic alcohol containing a homoallylic sulfone group represented by the formula (2).
Figure 112006012413348-pat00010
Figure 112006012413348-pat00010
 상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되며, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택된다.In the above formula, R 1 and R 2 are each selected from the group consisting of H, Me, Ph, and R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl. (a) 할로알릴릭 설폰 화합물 (E)를 인듐 중재 하에서 다양한 치환체를 함유하는 벤즈알데하이드 (F)와 반응시켜 화학식 2로 표시되는 호모알릴릭 설폰을 함유하는 호모알릴릭 알콜 화합물을 얻는 단계; 및 (a) reacting haloallylic sulfone compound (E) with benzaldehyde (F) containing various substituents under indium mediation to obtain a homoallylic alcohol compound containing homoallylic sulfone represented by formula (2); And (b) 화학식 2의 호모알릴릭 알콜과 상기 벤즈알데하이드 (F)와의 산성 조건에서 옥소니아-코프 재배열(oxonia-Cope rearrangement) 반응을 통해 알릴릭 설폰 화합물을 합성하는 단계를 포함하는 것을 특징으로 하는 화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰 화합물의 제조 방법.(b) synthesizing an allylic sulfone compound through an oxonia-cop rearrangement reaction in an acidic condition of the homoallylic alcohol of Formula 2 and the benzaldehyde (F). Method for producing an allylic sulfone compound containing a benzene ring represented by the formula (1).
Figure 112006012413348-pat00011
Figure 112006012413348-pat00011
 상기 식 중, R1과 R2는 각각 H, Me, Ph로 이루어진 군으로부터 선택되고, R3는 OMe, SMe, Me, H, Cl로 이루어진 군으로부터 선택되며, X는 Cl, Br, I로 이루어진 군으로부터 선택된다.Wherein R 1 and R 2 are each selected from the group consisting of H, Me and Ph, R 3 is selected from the group consisting of OMe, SMe, Me, H, Cl, and X is Cl, Br, I Selected from the group consisting of: 청구항 4은(는) 설정등록료 납부시 포기되었습니다.Claim 4 was abandoned when the registration fee was paid. 제3항에 있어서, 상기 (a)단계가, 물 또는 에틸알콜과 같은 극성 용매를 이용하거나, THF, DMF 또는 CH2Cl2와 같은 유기 용매와 물과의 혼합 용매를 사용하여, 20℃~120℃의 온도로 진행되는 것을 특징으로 하는 화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰 화합물의 제조 방법.The method of claim 3, wherein the step (a) is performed using a polar solvent such as water or ethyl alcohol, or a mixed solvent of water and an organic solvent such as THF, DMF or CH 2 Cl 2 , at a temperature of 20 ° C. to 5 ° C. Process for producing an allylic sulfone compound containing a benzene ring represented by the formula (1), characterized in that proceeds to a temperature of 120 ℃. 청구항 5은(는) 설정등록료 납부시 포기되었습니다.Claim 5 was abandoned upon payment of a set-up fee. 제3항에 있어서, 상기 (b)단계가, ZnCl2, BF3·OEt2, ZnBr2와 같은 루이스산(Lewis acid)을 이용하거나, 파라-톨루엔설폰산(p-toluenesulfonic acid), 켐포설폰산(10-camphorsulfonic acid)과 같은 유기산 또는 HCl 수용액과 같은 무기산(mineral acid)을 이용하고, CH2Cl2, ClCH2CH2Cl, benzene, toluene과 같은 유기용매 또는 물(H2O)에서 40℃~120℃의 온도로 진행되는 것을 특징으로 하는 화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰 화합물의 제조 방법.The method of claim 3, wherein the step (b) uses Lewis acid such as ZnCl 2 , BF 3 · OEt 2 , ZnBr 2 , or para-toluenesulfonic acid ( p- toluenesulfonic acid), chemposul Using an organic acid such as phenolic acid (10-camphorsulfonic acid) or a mineral acid such as aqueous HCl solution, and in organic solvents such as CH 2 Cl 2 , ClCH 2 CH 2 Cl, benzene, toluene or water (H 2 O) A process for producing an allylic sulfone compound containing a benzene ring represented by the formula (1), characterized in that it proceeds at a temperature of 40 ℃ ~ 120 ℃. 청구항 6은(는) 설정등록료 납부시 포기되었습니다.Claim 6 was abandoned when the registration fee was paid. 제3항에 있어서, R1 메틸 치환체를 갖는 할로알릴릭 설폰 화합물 (E)를 이용하여 알콜기와 설폰기가 반대 방향으로 배열된 안티(anti) 입체 구조의 화학식 2를 제조하고, 이로부터 R1과 R2를 함유하는 이중결합이 트랜스(trans) 구조를 갖는 알릴릭 설폰 화합물을 제조하는 단계를 포함하는 것을 특징으로 하는 화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰 화합물의 제조 방법.Of claim 3 wherein, R 1 methyl using the halo-allyl rigs sulfone compound (E) having a substituent and an alcohol group and a sulfonic group producing the anti (anti) formula (2) of the three-dimensional structure arranged in the opposite direction, from which R 1 and A method for producing an allylic sulfone compound containing a benzene ring represented by the formula (1), wherein the double bond containing R 2 comprises preparing an allylic sulfone compound having a trans structure. 청구항 7은(는) 설정등록료 납부시 포기되었습니다.Claim 7 was abandoned upon payment of a set-up fee. 제3항에 있어서, R1 페닐 치환체를 갖는 할로알릴릭 설폰 화합물 (E)를 이용하여 알콜기와 설폰기가 같은 방향으로 배열된 씬(syn) 입체 구조의 화학식 2를 제조하고, 이로부터 R1과 R2를 함유하는 이중결합이 씨스(cis) 구조를 갖는 알릴릭 설폰 화합물을 제조하는 단계를 포함하는 것을 특징으로 하는 화학식 1로 표시되는 벤젠 고리를 함유하는 알릴릭 설폰 화합물의 제조 방법.According to claim 3, using the haloallylic sulfone compound (E) having a R 1 phenyl substituent to prepare a general formula (2) of the syn ( Syn ) structure in which the alcohol group and sulfone groups are arranged in the same direction, from which R 1 and A method for producing an allylic sulfone compound containing a benzene ring represented by the formula (1), wherein the double bond containing R 2 comprises preparing an allylic sulfone compound having a cis structure.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4886916A (en) 1987-03-17 1989-12-12 Kuraray Company, Ltd. Process for preparing sulfone compounds
KR20030036057A (en) * 2001-10-31 2003-05-09 구상호 Method of preparing 4-chloro-3-methyl-2-butenylphenyl sulfide, di(4-chloro-3-methyl-2-butenyl) sulfide and di(4-chloro-3-methyl-2-butenyl) sulfone for synthesis of natural carotenoid products

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4886916A (en) 1987-03-17 1989-12-12 Kuraray Company, Ltd. Process for preparing sulfone compounds
KR20030036057A (en) * 2001-10-31 2003-05-09 구상호 Method of preparing 4-chloro-3-methyl-2-butenylphenyl sulfide, di(4-chloro-3-methyl-2-butenyl) sulfide and di(4-chloro-3-methyl-2-butenyl) sulfone for synthesis of natural carotenoid products
KR20050077504A (en) * 2001-10-31 2005-08-02 구상호 Method of preparing di(4-chloro-3-methyl-2-butenyl) sulfone for synthesis of natural carotenoid products

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