KR101035712B1 - 1,6-Dioxecanes and process for preparing them - Google Patents

1,6-Dioxecanes and process for preparing them Download PDF

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KR101035712B1
KR101035712B1 KR1020090053364A KR20090053364A KR101035712B1 KR 101035712 B1 KR101035712 B1 KR 101035712B1 KR 1020090053364 A KR1020090053364 A KR 1020090053364A KR 20090053364 A KR20090053364 A KR 20090053364A KR 101035712 B1 KR101035712 B1 KR 101035712B1
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dioxane
tetramethylene
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조용서
김유승
민선준
이재균
배애님
추현아
푼나 레디 울라프
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한국과학기술연구원
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    • C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

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Abstract

본 발명은 1,6-디옥세케인 화합물과 이의 제조방법에 관한 것으로서, 더욱 상세하게는 알렌닐 알코올 또는 알릴 알코올 화합물을 알데하이드 화합물과 루이스산 존재하에서 프린스 고리화 반응을 수행하여 제조된 하기 화학식 1로 표시되는 1,6-디옥세케인 화합물과 이 화합물의 제조방법에 관한 것이다. The present invention relates to a 1,6-dioxane compound and a method for preparing the same, and more particularly, to an allenyl alcohol or an allyl alcohol compound, which is prepared by performing a prince cyclization reaction in the presence of an aldehyde compound and a Lewis acid. It relates to a 1,6-dioxane compound represented by the formula and a method for producing the compound.

Figure 112009036319410-pat00001
Figure 112009036319410-pat00001

상기 화학식 1에서, R은 탄소수 5 내지 15의 아릴기, 또는 질소, 산소 및 황 원자 중에서 선택된 헤테로원자가 1 내지 3개 포함된 탄소수 5 내지 15의 헤테로아릴기를 나타내며; n은 0 또는 1을 나타낸다.In Formula 1, R represents an aryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 15 carbon atoms containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms; n represents 0 or 1.

1,6-디옥세케인, 알렌닐 알코올, 알릴 알코올, 루이스산, 프린스반응 1,6-dioxane, allenyl alcohol, allyl alcohol, Lewis acid, prince reaction

Description

1,6-디옥세케인 화합물과 이의 제조방법{1,6-Dioxecanes and process for preparing them}1,6-Dioxane compound and preparation method thereof {1,6-Dioxecanes and process for preparing them}

본 발명은 1,6-디옥세케인 화합물과 이의 제조방법에 관한 것으로서, 더욱 상세하게는 알렌닐 알코올 또는 알릴 알코올 화합물을 알데하이드 화합물과 루이스산 존재하에서 프린스 고리화 반응을 수행하여 제조된 하기 화학식 1로 표시되는 1,6-디옥세케인 화합물과 이 화합물의 제조방법에 관한 것이다. The present invention relates to a 1,6-dioxane compound and a method for preparing the same, and more particularly, to an allenyl alcohol or an allyl alcohol compound, which is prepared by performing a prince cyclization reaction in the presence of an aldehyde compound and a Lewis acid. It relates to a 1,6-dioxane compound represented by the formula and a method for producing the compound.

[화학식 1][Formula 1]

Figure 112009036319410-pat00002
Figure 112009036319410-pat00002

상기 화학식 1에서, R은 탄소수 5 내지 15의 아릴기, 또는 질소, 산소 및 황 원자 중에서 선택된 헤테로원자가 1 내지 3개 포함된 탄소수 5 내지 15의 헤테로아릴기를 나타내며; n은 0 또는 1을 나타낸다. In Formula 1, R represents an aryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 15 carbon atoms containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms; n represents 0 or 1.

10각 헤테로고리 그룹은 천연물이나 의약품을 구성하는 중요한 모핵 구조이나, 10각 헤테로고리 구조의 합성이 쉽지 않아 이의 제조방법은 거의 알려져 있지 않다. 본 발명이 제안하는 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물은 10각 헤테로고리 그룹을 갖고 있으므로 다양한 반응을 통해 다양한 천연물 또는 의약품을 합성할 수 있는 중간체로 활용이 가능하다. 10각 헤테로고리 그룹을 갖는 화합물을 중간체로 사용하여 합성이 가능한 의약품으로는 간염치료에 효능이 있는 폴리갈롤라이드 (Angew. Chem. Int. Ed. 2006, 45, 6532)가 그 예이다. The pentagonal heterocyclic group is an important parent nucleus structure constituting a natural product or a drug, but the synthesis of the pentagonal heterocyclic structure is not easy, so a method of preparing the heterocyclic group is hardly known. Since the 1,6-diocecaine compound represented by Chemical Formula 1 proposed by the present invention has a 10-membered heterocyclic group, it can be used as an intermediate capable of synthesizing various natural products or medicines through various reactions. An example of a drug that can be synthesized using a compound having a pentagonal heterocyclic group as an intermediate is polygalolide (Angew. Chem. Int. Ed . 2006 , 45, 6532), which is effective in treating hepatitis.

더욱이 본 발명이 제안하는 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물은 10각 헤테로고리 구조에 2 ~ 4개의 엑소메틸렌 그룹을 갖고 있으므로, 디엘스-올더(Diels-Alder) 반응을 통해 또 다른 다중고리 화합물을 합성하기 위한 중간체로서 매우 유용하게 사용될 수 있다.Furthermore, since the 1,6-dioxane compound represented by Chemical Formula 1 proposed by the present invention has 2 to 4 exomethylene groups in a 10-membered heterocyclic structure, the Diels-Alder reaction is used. It can be very usefully used as an intermediate for synthesizing another polycyclic compound.

본 발명은 천연물 또는 의약품의 중간체로서 유용한 신규 구조의 10각형 헤테로고리 화합물을 제공하는 것을, 발명이 해결하고자 하는 과제로 한다.The present invention is to provide a pentagonal heterocyclic compound having a novel structure useful as an intermediate of natural products or pharmaceuticals, the object of the present invention is to solve.

본 발명은 간편한 합성법으로 용이하게 제조가 가능한 10각형 헤테로고리 화합물의 제조방법을 제공하는 것을, 발명이 해결하고자 하는 과제로 한다.The present invention is to provide a method for producing a 10-membered heterocyclic compound that can be easily produced by a simple synthesis method, it is an object of the present invention to solve.

본 발명은 하기 화학식 1로 표시되는 1,6-디옥세케인 화합물을 제공함으로써, 본 발명의 과제를 해결한다.This invention solves the subject of this invention by providing the 1, 6- dioxane compound represented by following General formula (1).

[화학식 1][Formula 1]

Figure 112009036319410-pat00003
Figure 112009036319410-pat00003

상기 화학식 1에서, R은 탄소수 5 내지 15의 아릴기, 또는 질소, 산소 및 황 원자 중에서 선택된 헤테로원자가 1 내지 3개 포함된 탄소수 5 내지 15의 헤테로아릴기를 나타내며; n은 0 또는 1을 나타낸다.In Formula 1, R represents an aryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 15 carbon atoms containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms; n represents 0 or 1.

또한, 본 발명은 하기 반응식 1에 나타낸 바와 같이, 하기 화학식 2로 표시되는 알코올 화합물과 하기 화학식 3으로 표시되는 알데하이드 화합물을 프린스 고리화 반응을 수행하여 하기 화학식 1로 표시되는 1,6-디옥세케인 화합물을 제조하는 방법을 제공함으로써, 본 발명의 과제를 해결한다.In addition, the present invention, as shown in the following Scheme 1, 1,6-diocece represented by the following formula 1 by performing a prince cyclization reaction of the alcohol compound represented by the formula (2) and the aldehyde compound represented by the formula (3) The problem of this invention is solved by providing the method of manufacturing a kane compound.

Figure 112009036319410-pat00004
Figure 112009036319410-pat00004

상기 반응식 1에서, R은 탄소수 6 내지 8의 아릴기, 또는 질소, 산소 및 황 원자 중에서 선택된 헤테로원자가 1 내지 3개 포함된 탄소수 4 내지 6의 헤테로아릴기를 나타내며; n은 0 또는 1을 나타낸다.In Scheme 1, R represents an aryl group having 6 to 8 carbon atoms or a heteroaryl group having 4 to 6 carbon atoms containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms; n represents 0 or 1.

이와 같은 본 발명을 보다 구체적으로 설명하면 다음과 같다.The present invention will be described in more detail as follows.

본 발명이 특징으로 하는 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물은 10원자의 헤테로고리(10-membered heterocyclic ring) 구조를 갖고 있으면서 2 내지 4개의 엑소메틸렌 그룹(exomethylene group)을 동시에 포함하고 있는 신규 구조의 화합물이다.The 1,6-dioxane compound represented by Chemical Formula 1, which is characterized by the present invention, has a 10-membered heterocyclic ring structure and simultaneously contains 2 to 4 exomethylene groups. It is a compound of the novel structure contained.

본 발명에 따른 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물의 정의에 사용된 '아릴'은 페닐, 바이페닐, 페닐-O-페닐, 나프틸, 안트라니릴, 페난트리닐 등을 포함하는 단일고리, 두고리, 또는 세고리 방향족 탄화수소기를 의미한다. 또한, 상기한 아릴은 할로겐원자, CN, OH, NO2, 케톤(=O), COOH, COO-알킬, 알킬-COOH, 알킬-OH, 알킬, 할로알킬, O-알킬, O-할로알킬, NH2, NH(알킬), N(알킬)2로 이루어진 그룹으로부터 선택된 치환체가 0 내지 3개 치환될 수도 있다. 'Aryl' used in the definition of the 1,6-dioxane compound represented by Formula 1 according to the present invention includes phenyl, biphenyl, phenyl-O-phenyl, naphthyl, anthranilyl, phenanthryl, and the like. Means a monocyclic, bicyclic, or tricyclic aromatic hydrocarbon group. In addition, the aryl is a halogen atom, CN, OH, NO 2 , ketone (= O), COOH, COO-alkyl, alkyl-COOH, alkyl-OH, alkyl, haloalkyl, O-alkyl, O-haloalkyl, 0 to 3 substituents selected from the group consisting of NH 2 , NH (alkyl), N (alkyl) 2 may be substituted.

본 발명에 따른 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물의 정의에 사용된 '헤테로아릴'은 N, O 및 S 중에서 선택된 헤테로원자가 1 내지 3개 포함되어 단일고리, 두고리 또는 세고리로 이루어진 탄소수 5 내지 15의 방향족 헤테로탄화수소기를 포함한다. 상기한 헤테로아릴기는 구체적으로 피롤일, 퓨란일, 싸이오페닐, 피라졸릴, 이미다졸릴, 옥사졸일, 아이소옥사졸일, 싸이아졸일, 아이소타이아졸일, 트라이아졸일, 옥사다이아졸일, 싸이아다이아졸일, 테트라졸일릴, 피 리디닐, 피라지닐, 트리아지닐, 피리다지닐, 피리미디닐, 트라이아졸일, 인돌일, 인돌리지닐, 아이소인돌일, 벤조퓨릴, 벤조퓨라자닐, 다이벤조퓨릴, 아이소벤조퓨릴, 인다졸일, 벤즈이미다졸일, 이미다조피리디닐, 벤즈옥사졸일, 벤즈아이스옥사졸일, 벤조싸이아졸일, 다이벤조싸이오페닐, 나프티리딜, 벤즈아이소싸이아졸일, 퀴놀리닐, 아이소퀴놀리닐, 퀴녹살리일, 프탈라지닐, 치놀리닐, 퀴나졸리닐, 카바졸릴, 페나지닐, 페녹티아지닐, 또는 아크리디닐 등을 포함할 수 있다. 또한 상기한 헤테로아릴은 할로겐원자, CN, OH, NO2, 케톤(=O), COOH, COO-알킬, 알킬-COOH, 알킬-OH, 알킬, 할로알킬, O-알킬, O-할로알킬, NH2, NH(알킬), N(알킬)2, NHC(O)(알킬), S-알킬, C(O)-알킬, C(O)-할로알킬, C(O)-NH2, C(O)-NH(알킬), 및 C(O)-N(알킬)2 으로 이루어진 그룹으로부터 선택된 치환체가 0 내지 3개 치환될 수도 있다.'Heteroaryl' used in the definition of the 1,6-dioxane compound represented by Chemical Formula 1 according to the present invention includes one to three heteroatoms selected from N, O and S, and may be monocyclic, bicyclic or tricyclic. It includes an aromatic heterohydrocarbon group having 5 to 15 carbon atoms. The heteroaryl group described above may specifically be pyrroyl, furanyl, thiophenyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, oxadiazolyl, thi Adiazolyl, tetrazolyl, pyridinyl, pyrazinyl, triazinyl, pyridazinyl, pyrimidinyl, triazolyl, indolyl, indolinyl, isoindolyl, benzofuryl, benzofurazilyl, di Benzofuryl, isobenzofuryl, indazolyl, benzimidazolyl, imidazopyridinyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, dibenzothiophenyl, naphthyridyl, benzisothiazylyl, Quinolinyl, isoquinolinyl, quinoxalyl, phthalazinyl, chinolinyl, quinazolinyl, carbazolyl, phenazinyl, phenoxthiazinyl, acridinyl, and the like. In addition, the heteroaryl may be a halogen atom, CN, OH, NO 2 , ketone (= O), COOH, COO-alkyl, alkyl-COOH, alkyl-OH, alkyl, haloalkyl, O-alkyl, O-haloalkyl, NH 2 , NH (alkyl), N (alkyl) 2 , NHC (O) (alkyl), S-alkyl, C (O) -alkyl, C (O) -haloalkyl, C (O) -NH 2 , C 0 to 3 substituents selected from the group consisting of (O) -NH (alkyl), and C (O) -N (alkyl) 2 may be substituted.

상기 치환체 정의에 사용된 알킬은 메틸, 에틸, n-프로필, i-프로필, 싸이클로프로필, n-부틸, i-부틸, t-부틸, 싸이클로부틸, 싸이클로프로필메틸, n-펜틸, i-펜틸, 네오펜틸, t-펜틸, 싸이클로펜틸, 싸이클로부틸메틸, n-헥실, i-헥실, 싸이클로헥실, 싸이클로펜틸메틸, 헵틸, 싸이클로헥실메틸, 옥틸 등을 포함하는 1개에서 10개까지의 탄소원자를 가지는 직쇄상, 분쇄상 또는 고리상의 지방족 포화 탄화수소기를 의미한다. Alkyl used in this substituent definition is methyl, ethyl, n -propyl, i -propyl, cyclopropyl, n -butyl, i -butyl, t -butyl, cyclobutyl, cyclopropylmethyl, n -pentyl, i -pentyl, Having from 1 to 10 carbon atoms including neopentyl, t -pentyl, cyclopentyl, cyclobutylmethyl, n -hexyl, i -hexyl, cyclohexyl, cyclopentylmethyl, heptyl, cyclohexylmethyl, octyl, etc. Linear, pulverized or cyclic aliphatic saturated hydrocarbon groups.

상기 화학식 1로 표시되는 1,6-디옥세케인 화합물에 있어, 바람직하기로는 상기 R가 페닐기; 할로, 탄소수 1 내지 6의 알킬, 및 탄소수 1 내지 6의 알콕시 중 에서 선택된 치환기가 1 내지 3개 치환된 페닐기; 티오펜일기; 또는 퓨란일기를 나타내고; n은 0 또는 1인 1,6-디옥세케인 화합물의 경우이다.In the 1,6-dioxane compound represented by the formula (1), Preferably R is a phenyl group; A phenyl group having 1 to 3 substituents selected from halo, alkyl having 1 to 6 carbon atoms, and alkoxy having 1 to 6 carbon atoms; Thiophenyl group; Or furanyl group; n is the case of a 1, 6- dioxane compound which is 0 or 1.

상기 화학식 1로 표시되는 1,6-디옥세케인 화합물에 있어, 특히 바람직하기로는 3,4,8,9-테트라메틸렌-2,7-다이페닐-1,6-디옥세케인, 2,7-비스(4-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인, 2,7-비스(2-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인, 2,7-비스(3-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인, 3,4,8,9-테트라메틸렌-2,7-디-파라-톨일-1,6-디옥세케인, 2,7-비스(4-플로로페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인, 2,7-비스(4-클로로페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인, 3,4,8,9-테트라메틸렌-2,7-디(티오펜-2-일)-1,6-디옥세케인, 4,9-디메틸렌-2,7-디페닐-1,6-디옥세케인, 2,7-비스(2-메톡시페닐)-4,9-디메틸렌-1,6-디옥세케인, 4,9-디메틸렌-2,7-디(메타-톨일)-1,6-디옥세케인, 2,7-비스(4-플로로페닐)-4,9-디메틸렌-1,6-디옥세케인, 4,9-디메틸렌-2,7-디(티오펜-2-일)-1,6-디옥세케인, 또는 2,7-디(퓨란-3-일)-4,9-디메틸렌-1,6-디옥세케인이다.In the 1,6-dioxane compound represented by the general formula (1), particularly preferably 3,4,8,9-tetramethylene-2,7-diphenyl-1,6-dioxane, 2,7 -Bis (4-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 2,7-bis (2-dimethoxyphenyl) -3,4,8,9- Tetramethylene-1,6-dioxane, 2,7-bis (3-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 3,4,8,9 -Tetramethylene-2,7-di-para-tolyl-1,6-dioxane, 2,7-bis (4-fluorophenyl) -3,4,8,9-tetramethylene-1,6- Dioxane, 2,7-bis (4-chlorophenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 3,4,8,9-tetramethylene-2,7- Di (thiophen-2-yl) -1,6-dioxane, 4,9-dimethylene-2,7-diphenyl-1,6-dioxane, 2,7-bis (2-methoxy Phenyl) -4,9-dimethylene-1,6-dioxane, 4,9-dimethylene-2,7-di (meth-tolyl) -1,6-dioxane, 2,7-bis ( 4-fluorophenyl) -4,9-dimethylene-1,6-dioxane, 4,9-dimethylene-2,7-di (thiophene-2- ) 1,6-okse Kane, or 2,7-di (furan-3-yl) a-4,9-dimethylene-1,6-okse Kane.

또한, 본 발명은 상기 화학식 2로 표시되는 알코올 화합물과 상기 화학식 3으로 표시되는 알데하이드 화합물을 출발물질로 사용한 프린스 고리화 반응에 의해, 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물을 제조하는 방법을 그 특징으로 한다.The present invention also provides a 1,6-diocecaine compound represented by Chemical Formula 1 by the Prince cyclization reaction using the alcohol compound represented by Chemical Formula 2 and the aldehyde compound represented by Chemical Formula 3 as starting materials. The method is characterized by.

본 발명의 프린스 고리화 반응은 루이스산 존재 하에서 수행되는데, 루이스산의 대표적인 예로서는 트리메틸실릴 트리플루오로메탄설포네이트(TMSOTf)를 사용 할 수 있다. 루이스 산은 상기 화학식 2로 표시되는 알코올 화합물에 대하여 0.1 내지 2 당량 범위내에서 사용할 수 있다. 본 발명의 프린스 고리화 반응에서는 용매로서 통상의 유기용매를 사용할 수 있으며, 그 중 바람직하기로는 테트라하이드퓨란을 용매로 사용하는 것이다. 본 발명의 프린스 고리화 반응온도는 -78 ℃ 내지 30 ℃ 범위를 유지하도록 하며, 반응시간은 대략 5 내지 7시간이면 충분하다.Prince cyclization reaction of the present invention is carried out in the presence of Lewis acid, a representative example of Lewis acid may be used trimethylsilyl trifluoromethanesulfonate (TMSOTf). Lewis acid can be used within the range of 0.1 to 2 equivalents relative to the alcohol compound represented by the formula (2). In the prince cyclization reaction of the present invention, a conventional organic solvent can be used as a solvent, and among these, tetrahydrofuran is preferably used as a solvent. Prince cyclization reaction temperature of the present invention is to maintain the range -78 ℃ to 30 ℃, the reaction time is approximately 5 to 7 hours is sufficient.

이상에서 설명한 바와 같은 본 발명은 하기 실시예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 하기 실시예에 의해 한정되는 것은 아니다.The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited by the following examples.

실시예 1 : 3,4,8,9-테트라메틸렌-2,7-다이페닐-1,6-디옥세케인의 합성Example 1 Synthesis of 3,4,8,9-tetramethylene-2,7-diphenyl-1,6-dioxane

Figure 112009036319410-pat00005
Figure 112009036319410-pat00005

건조된 테트라하이드퓨란 (6.0 mL)에 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol과 벤즈알데하이드 0.45 mmol을 넣고 -78 ℃로 냉각시킨 후, 루이산인 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 가하고 7시간 동안 서서히 상온으로 올려주었다. 반응용액에 NaHCO3의 수용액을 넣은 후 다이에틸이서로 묽혀 준 후, 유기층을 물과 소금물로 씻어주고 MgSO4로 건조시키고, 여과 및 농축시켜 관 크로마토그래피를 이용하여 73% 수율로 순수한 표제화합물을 얻었다. 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol and 0.45 mmol of benzaldehyde were added to dried tetrahydrofuran (6.0 mL), and cooled to -78 ° C. 0.45 mmol of methylsalyltriplate (TMSOTf) was added and slowly raised to room temperature for 7 hours. After adding an aqueous solution of NaHCO 3 to the reaction solution and diluting with diethyl ether, the organic layer was washed with water and brine, dried over MgSO 4 , filtered and concentrated to give pure title compound in 73% yield using column chromatography. Got it.

흰색 고체; m.p. 170-171 ℃; 1H NMR (400 MHz, CDCl3) δ 7.40-7.29 (m, 10H), 5.38 (s, 2H), 5.28 (s, 2H), 5.13 (s, 2H), 4.91 (s, 2H), 4.71 (s, 2H), 4.35 (d, 2H, J = 11.2 Hz), 4.13 (d, 2H, J = 10.8 Hz) 13C NMR (100 MHz, CDCl3) δ 150.85, 146.02, 139.78, 128.18, 127.41, 127.30, 118.08, 117.80, 81.68, 71.84 IR (thin film) 3058, 2958, 1629, 1209, 1110 cm-1 White solid; mp 170-171 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.40-7.29 (m, 10H), 5.38 (s, 2H), 5.28 (s, 2H), 5.13 (s, 2H), 4.91 (s, 2H), 4.71 ( s, 2H), 4.35 (d, 2H, J = 11.2 Hz), 4.13 (d, 2H, J = 10.8 Hz) 13 C NMR (100 MHz, CDCl 3 ) δ 150.85, 146.02, 139.78, 128.18, 127.41, 127.30 , 118.08, 117.80, 81.68, 71.84 IR (thin film) 3058, 2958, 1629, 1209, 1110 cm -1

실시예 2 : 2,7-비스(4-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인의 합성Example 2 Synthesis of 2,7-bis (4-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane

Figure 112009036319410-pat00006
Figure 112009036319410-pat00006

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 4-메톡시벤즈알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 55% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of 4-methoxybenzaldehyde, and trimethylsalyltriplate ( TMSOTf) 0.45 mmol was used to give the pure title compound in 55% yield.

오일상태; 1H NMR (400 MHz, CDCl3) δ 7.28 (d, 4H, J = 4.4 Hz), 6.90 (d, 4H, J = 6.8 Hz), 5.23 (d, 2H, J = 2.4 Hz), 5.48 (t, 2H, J = 2.2 Hz), 5.33 (s, 2H), 5.01 (s, 2H), 4.67 (d, 2H, J = 1.6 Hz), 4.64 (t, 2H, J = 2.2 Hz), 4.53-5.49 (m, 2H), 3.82 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 159.49, 148.51, 144.80, 133.03, 128.86, 113.82, 105.49, 102.73, 84.36, 71.32, 55.28 IR (thin film) 2934, 1725, 1610, 1509, 1250, 1030 cm-1 Oil state; 1 H NMR (400 MHz, CDCl 3 ) δ 7.28 (d, 4H, J = 4.4 Hz), 6.90 (d, 4H, J = 6.8 Hz), 5.23 (d, 2H, J = 2.4 Hz), 5.48 (t , 2H, J = 2.2 Hz), 5.33 (s, 2H), 5.01 (s, 2H), 4.67 (d, 2H, J = 1.6 Hz), 4.64 (t, 2H, J = 2.2 Hz), 4.53-5.49 (m, 2 H), 3.82 (s, 6 H); 13 C NMR (100 MHz, CDCl 3) δ 159.49, 148.51, 144.80, 133.03, 128.86, 113.82, 105.49, 102.73, 84.36, 71.32, 55.28 IR (thin film) 2934, 1725, 1610, 1509, 1250, 1030 cm - One

실시예 3 : 2,7-비스(2-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인의 합성Example 3 Synthesis of 2,7-bis (2-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane

Figure 112009036319410-pat00007
Figure 112009036319410-pat00007

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 2-메톡시벤즈알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 50% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of 2-methoxybenzaldehyde, and trimethylsalyltriplate ( TMSOTf) 0.45 mmol was used to give the pure title compound in 50% yield.

흰고체; m.p. 172-173 ℃; 1H NMR (400 MHz, CDCl3) δ 7.33-7.28 (m, 4H), 6.93 (dd, 4H, J = 7.8, 10.0 Hz), 5.88 (s, 2H), 5.47 (m, 4H), 5.00 (s, 2H), 4.79 (s, 2H), 4.68 (d, 2H, J = 12.8 Hz), 4.54 (d, 2H,J = 12.8 Hz), 3.86 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 157.12, 147.70, 145.13, 129.71, 128.98, 127.89, 120.72, 110.70, 104.85, 102.34, 78.85, 71.59, 55.51 ; IR (thin film) 2935, 2837, 1600, 1242, 1048 cm-1 White solid; mp 172-173 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.33-7.28 (m, 4H), 6.93 (dd, 4H, J = 7.8, 10.0 Hz), 5.88 (s, 2H), 5.47 (m, 4H), 5.00 ( s, 2H), 4.79 (s, 2H), 4.68 (d, 2H, J = 12.8 Hz), 4.54 (d, 2H, J = 12.8 Hz), 3.86 (s, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ 157.12, 147.70, 145.13, 129.71, 128.98, 127.89, 120.72, 110.70, 104.85, 102.34, 78.85, 71.59, 55.51; IR (thin film) 2935, 2837, 1600, 1242, 1048 cm -1

실시예 4. 2,7-비스(3-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인의 합성Example 4 Synthesis of 2,7-bis (3-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane

Figure 112009036319410-pat00008
Figure 112009036319410-pat00008

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 3-메톡시벤즈알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 83% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of 3-methoxybenzaldehyde, and trimethylsalyltriplate ( TMSOTf) 0.45 mmol was used to obtain the pure title compound in 83% yield.

흰고체; m.p. 171-172 ℃; 1H NMR (400 MHz, CDCl3) δ 7.29-7.26 (m,4H), 6.96-6.94 (m, 4H), 6.84 (dd, 2H, J = 4.0, 0.8 Hz), 5.38 (s, 2H), 5.25 (d, 2H, J = 1.6 Hz), 5.15 (d, 2H, J = 1.6 Hz), 4.91 (s, 2H), 4.74 (s, 2H), 4.29 (d, 2H, J = 11.2 Hz), 4.14 (d, 2H, J = 11.2 Hz), 3.82 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 159.60, 150.83, 145.93, 141.39, 129.15, 119.97, 118.29, 117.64, 112.99, 112.76, 81.23, 71.87, 55.21 IR (thin film) 2999, 2916, 1602, 1491, 1253, 1107, 923 cm-1 White solid; mp 171-172 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.29-7.26 (m, 4H), 6.96-6.94 (m, 4H), 6.84 (dd, 2H, J = 4.0, 0.8 Hz), 5.38 (s, 2H), 5.25 (d, 2H, J = 1.6 Hz), 5.15 (d, 2H, J = 1.6 Hz), 4.91 (s, 2H), 4.74 (s, 2H), 4.29 (d, 2H, J = 11.2 Hz), 4.14 (d, 2H, J = 11.2 Hz), 3.82 (s, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ 159.60, 150.83, 145.93, 141.39, 129.15, 119.97, 118.29, 117.64, 112.99, 112.76, 81.23, 71.87, 55.21 IR (thin film) 2999, 2916, 1602, 1491, 1253 , 1107, 923 cm -1

실시예 5. 3,4,8,9-테트라메틸렌-2,7-디-파라-톨일-1,6-디옥세케인의 합성Example 5 Synthesis of 3,4,8,9-tetramethylene-2,7-di-para-tolyl-1,6-dioxane

Figure 112009036319410-pat00009
Figure 112009036319410-pat00009

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 파라-토루알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 75% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of para-tolualdehyde, and trimethylsalyltriplate (TMSOTf) 0.45 mmol was used to yield the pure title compound in 75% yield.

흰고체; m.p. 196-197 ℃; 1H NMR (400 MHz, CDCl3) δ 7.25 (d, 4H, J = 8.0 Hz), 7.18 (d, 4H, J = 8.0 Hz), 5.24 (d, 2H, 2.4 Hz), 5.48(t, 2H, J = 2.4 Hz), 5.35(s, 2H), 5.02 (s, 2H), 4.70-4.65 (m, 4H), 4.56 (tt, 2H,J = 12.8, 2.4 Hz), 2.36 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 148.43, 144.77, 138.00, 137.78, 129.13, 127.34, 105.45, 102.74, 84.53, 71.44, 21.20 ; IR (thin film) 2920, 1665, 1513, 1451, 1047 cm-1 White solid; mp 196-197 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.25 (d, 4H, J = 8.0 Hz), 7.18 (d, 4H, J = 8.0 Hz), 5.24 (d, 2H, 2.4 Hz), 5.48 (t, 2H , J = 2.4 Hz), 5.35 (s, 2H), 5.02 (s, 2H), 4.70-4.65 (m, 4H), 4.56 (tt, 2H, J = 12.8, 2.4 Hz), 2.36 (s, 6H) ; 13 C NMR (100 MHz, CDCl 3 ) δ 148.43, 144.77, 138.00, 137.78, 129.13, 127.34, 105.45, 102.74, 84.53, 71.44, 21.20; IR (thin film) 2920, 1665, 1513, 1451, 1047 cm -1

실시예 6. 2,7-비스(4-플로로페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인의 합성Example 6 Synthesis of 2,7-bis (4-fluorophenyl) -3,4,8,9-tetramethylene-1,6-dioxane

Figure 112009036319410-pat00010
Figure 112009036319410-pat00010

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 파라-플로로알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 85% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of para-fluoroaldehyde, and trimethylsalyltriplate (TMSOTf 0.45 mmol was used to give the pure title compound in 85% yield.

흰고체; m.p. 121-122 ℃; 1H NMR (400 MHz, CDCl3) δ 7.33 (dd, 4H, J = 5.6, 2.8 Hz), 7.04 (t, 4H, J = 8.6 Hz), 5.30 (s, 4H), 5.09 (d, 2H, J = 2 Hz), 4.91 (s, 2H), 4.75 (s, 2H), 4.34 (d, 2H, J = 10.8 Hz), 4.07 (d, 2H, J = 10.8 Hz); 13C NMR (100 MHz, CDCl3) δ 163.34, 150.39, 145.78, 135.50, 128.73, 128.67, 118.10, 118.06, 81.37, 71.70 ; IR (thin film) 3079, 2932, 1632, 1506, 1209, 1087, 917 cm-1 White solid; mp 121-122 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.33 (dd, 4H, J = 5.6, 2.8 Hz), 7.04 (t, 4H, J = 8.6 Hz), 5.30 (s, 4H), 5.09 (d, 2H, J = 2 Hz), 4.91 (s, 2H), 4.75 (s, 2H), 4.34 (d, 2H, J = 10.8 Hz), 4.07 (d, 2H, J = 10.8 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ 163.34, 150.39, 145.78, 135.50, 128.73, 128.67, 118.10, 118.06, 81.37, 71.70; IR (thin film) 3079, 2932, 1632, 1506, 1209, 1087, 917 cm -1

실시예 7. 2,7-비스(4-클로로페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인의 합성Example 7 Synthesis of 2,7-bis (4-chlorophenyl) -3,4,8,9-tetramethylene-1,6-dioxane

Figure 112009036319410-pat00011
Figure 112009036319410-pat00011

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 파라-클로로알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 76% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of para-chloroaldehyde, and trimethylsalyltriplate (TMSOTf) 0.45 mmol of pure title compound was obtained in 76% yield.

흰고체; m.p. 201-202 ℃; 1H NMR (400 MHz, CDCl3) δ 7.3-7.28 (m, 8H), 5.31 (d, 2H, J = 2 Hz), 5.25 (s, 2H), 5.07 (d, 2H, J = 2 Hz), 4.91 (s, 2H), 4.79 (s, 2H), 4.36 (d, 2H, J = 10.8 Hz), 4.05 (d, 2H, J = 10.8 Hz); 13C NMR (100 MHz, CDCl3) δ 149.92, 145.62, 138.36, 133.07, 128.37, 118.43, 118.13, 81.52, 71.69. ; IR (thin film) 3086, 2924, 1632, 1489, 1087, 739 cm-1 White solid; mp 201-202 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.3-7.28 (m, 8H), 5.31 (d, 2H, J = 2 Hz), 5.25 (s, 2H), 5.07 (d, 2H, J = 2 Hz) , 4.91 (s, 2H), 4.79 (s, 2H), 4.36 (d, 2H, J = 10.8 Hz), 4.05 (d, 2H, J = 10.8 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ 149.92, 145.62, 138.36, 133.07, 128.37, 118.43, 118.13, 81.52, 71.69. ; IR (thin film) 3086, 2924, 1632, 1489, 1087, 739 cm -1

실시예 8 : 3,4,8,9-테트라메틸렌-2,7-디(티오펜-2-일)-1,6-디옥세케인의 합성Example 8 Synthesis of 3,4,8,9-tetramethylene-2,7-di (thiophen-2-yl) -1,6-dioxane

Figure 112009036319410-pat00012
Figure 112009036319410-pat00012

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.45 mmol, 2-티아펜카바알데하이드 0.45 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.45 mmol을 사용하여 50% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.45 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.45 mmol of 2-thiaphencarbaaldehyde, and trimethylsalyltriplate ( TMSOTf) 0.45 mmol was used to give the pure title compound in 50% yield.

오일; 1H NMR (400 MHz, CDCl3) δ 7.31 (d, 2H, J = 5.2 Hz), 7.07 (d, 2H, J = 3.2 Hz), 6.98 (dd, 2H, J = 4.8, 1.2 Hz), 5.70 (s, 2H), 5.59 (d, 2H, J = 2Hz), 5.51 (t, 2H, J =2.4 Hz), 5.0 (s, 2H), 4.94 (s, 2H), 4.65 (d, 2H, J = 13.2 Hz), 4.53 (d, 2H, J = 12.8 Hz) 13C NMR (100 MHz, CDCl3) δ 147.40, 144.37, 143.87, 126.53, 125.99, 125.79, 105.91, 103.33, 80.15, 71.22 ; IR (thin film) 2924, 2852, 1640, 1261, 1036 cm-1 oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.31 (d, 2H, J = 5.2 Hz), 7.07 (d, 2H, J = 3.2 Hz), 6.98 (dd, 2H, J = 4.8, 1.2 Hz), 5.70 (s, 2H), 5.59 (d, 2H, J = 2 Hz), 5.51 (t, 2H, J = 2.4 Hz), 5.0 (s, 2H), 4.94 (s, 2H), 4.65 (d, 2H, J = 13.2 Hz), 4.53 (d, 2H, J = 12.8 Hz) 13 C NMR (100 MHz, CDCl 3 ) δ 147.40, 144.37, 143.87, 126.53, 125.99, 125.79, 105.91, 103.33, 80.15, 71.22; IR (thin film) 2924, 2852, 1640, 1261, 1036 cm -1

실시예 9 : 4,9-디메틸렌-2,7-디페닐-1,6-디옥세케인의 합성Example 9: Synthesis of 4,9-dimethylene-2,7-diphenyl-1,6-dioxane

Figure 112009036319410-pat00013
Figure 112009036319410-pat00013

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.485 mmol, 벤즈알데하이드 0.485 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.485 mmol을 사용하여 72% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.485 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.485 mmol of benzaldehyde, and 0.485 mmol of trimethylsalyltriplate (TMSOTf) The pure title compound was obtained in 72% yield using.

실시예 10 : 2,7-비스(2-메톡시페닐)-4,9-디메틸렌-1,6-디옥세케인의 합성Example 10 Synthesis of 2,7-bis (2-methoxyphenyl) -4,9-dimethylene-1,6-dioxane

Figure 112009036319410-pat00014
Figure 112009036319410-pat00014

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.485 mmol, 2-메톡시벤즈알데하이드 0.485 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.485 mmol을 사용하여 74% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.485 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.485 mmol of 2-methoxybenzaldehyde, and trimethylsalyltriplate ( TMSOTf) 0.485 mmol gave the pure title compound in 74% yield.

오일; 1H NMR (400 MHz, CDCl3) δ 7.48 (d, 2H, J = 7.6 Hz), 7.27-7.23 (m, 2H), 6.97 (t, 2H, J = 7.6 Hz), 6.88 (d, 2H, 8 Hz), 5.27 (t, 2H, J = 7.4 Hz), 4.99 (m, 2H), 4.95 (m, 2H), 4.62 (d, 2H, J = 12.8 Hz), 4.40 (d, 2H, J = 13.2 Hz), 3.84 (s, 6H), 3.08-3.03 (m, 2H), 2.46-2.40 (m, 2H) 13C NMR (100 MHz, CDCl3) δ 156.25, 148.45, 130.70, 128.17, 125.68, 120.56, 110.09, 104.07, 71.19, 55.28, 39.90; IR (thin film) 2836, 1602, 1492, 1244, 1058, 754 cm-1 oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.48 (d, 2H, J = 7.6 Hz), 7.27-7.23 (m, 2H), 6.97 (t, 2H, J = 7.6 Hz), 6.88 (d, 2H, 8 Hz), 5.27 (t, 2H, J = 7.4 Hz), 4.99 (m, 2H), 4.95 (m, 2H), 4.62 (d, 2H, J = 12.8 Hz), 4.40 (d, 2H, J = 13.2 Hz), 3.84 (s, 6H), 3.08-3.03 (m, 2H), 2.46-2.40 (m, 2H) 13 C NMR (100 MHz, CDCl 3 ) δ 156.25, 148.45, 130.70, 128.17, 125.68, 120.56 , 110.09, 104.07, 71.19, 55.28, 39.90; IR (thin film) 2836, 1602, 1492, 1244, 1058, 754 cm -1

실시예 11 : 4,9-디메틸렌-2,7-디(메타-톨일)-1,6-디옥세케인의 합성Example 11: Synthesis of 4,9-dimethylene-2,7-di (meth-tolyl) -1,6-dioxane

Figure 112009036319410-pat00015
Figure 112009036319410-pat00015

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.485 mmol, 메타-톨일알데하이드 0.485 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.485 mmol을 사용하여 59% 수율로 순수한 표제화합물을 얻었다. 0.485 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.485 mmol of meta-tolylaldehyde, and trimethylsalyltriplate (TMSOTf) 0.485 mmol of the pure title compound was obtained in 59% yield.

흰고체; m.p. 188-190 ℃; 1H NMR (400 MHz, CDCl3) δ 7.29-7.25 (m, 2H), 7.18 (t, 4H, J = 8.0 Hz), 7.13 (d, 2H, J = 7.2 Hz), 5.23 (dd, 2H, J = 7.4 Hz), 5.15 (s, 2H), 4.89 (s, 2H), 4.25 (d, 2H, J = 12.0 Hz), 3.81 (d, 2H, J = 12.4 Hz), 2.61 (t, 2H, J = 13.6 Hz), 2.49 (d, 2H, J = 12.8 Hz), 2.39 (s, 6H) 13C NMR (100 MHz, CDCl3) δ 142.62, 141.75, 138.18, 128.42, 128.27, 127.38, 123.91, 120.24, 74.95, 72.02, 46.83, 21.53; IR (thin film) 3074, 2930, 2860,1642, 1083 cm-1 White solid; mp 188-190 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.29-7.25 (m, 2H), 7.18 (t, 4H, J = 8.0 Hz), 7.13 (d, 2H, J = 7.2 Hz), 5.23 (dd, 2H, J = 7.4 Hz), 5.15 (s, 2H), 4.89 (s, 2H), 4.25 (d, 2H, J = 12.0 Hz), 3.81 (d, 2H, J = 12.4 Hz), 2.61 (t, 2H, J = 13.6 Hz), 2.49 (d, 2H, J = 12.8 Hz), 2.39 (s, 6H) 13 C NMR (100 MHz, CDCl 3 ) δ 142.62, 141.75, 138.18, 128.42, 128.27, 127.38, 123.91, 120.24 , 74.95, 72.02, 46.83, 21.53; IR (thin film) 3074, 2930, 2860,1642, 1083 cm -1

실시예 12 : 2,7-비스(4-플로로페닐)-4,9-디메틸렌-1,6-디옥세케인의 합성Example 12 Synthesis of 2,7-bis (4-fluorophenyl) -4,9-dimethylene-1,6-dioxane

Figure 112009036319410-pat00016
Figure 112009036319410-pat00016

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.485 mmol, 4-플로로벤즈알데하이드 화합물 0.485 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.485 mmol을 사용하여 71% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.485 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.485 mmol of 4-fluorobenzaldehyde compound, and trimethylsalyltriplate (TMSOTf) 0.485 mmol gave the title compound in 71% yield.

흰고체; m.p. 221-223 ℃; 1H NMR (400 MHz, CDCl3) δ 7.36 (dd, 4H, J = 5.6 Hz), 7.07 (t, 4H, J = 6.8 Hz), 5.25 (dd, 2H, J = 8.0, 3.6 Hz), 5.15 (s, 2H), 4.87 (s, 2H), 4.23 (d, 2H, J = 12.4 Hz), 3.71 (d, 2H, J = 12.4 Hz), 2.58 (t, 2H, J = 8.0 Hz), 2.43 (d, 2H, J = 11.2 Hz); 13C NMR (100 MHz, CDCl3) δ 163.46, 141.33, 138.16, 128.36, 128.28, 120.46,115.57, 115.36, 74.24, 71.89, 46.81; IR (thin film) 3078, 2924, 1601, 1508, 1220, 1081 cm-1 White solid; mp 221-223 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.36 (dd, 4H, J = 5.6 Hz), 7.07 (t, 4H, J = 6.8 Hz), 5.25 (dd, 2H, J = 8.0, 3.6 Hz), 5.15 (s, 2H), 4.87 (s, 2H), 4.23 (d, 2H, J = 12.4 Hz), 3.71 (d, 2H, J = 12.4 Hz), 2.58 (t, 2H, J = 8.0 Hz), 2.43 (d, 2H, J = 11.2 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ 163.46, 141.33, 138.16, 128.36, 128.28, 120.46,115.57, 115.36, 74.24, 71.89, 46.81; IR (thin film) 3078, 2924, 1601, 1508, 1220, 1081 cm -1

실시예 13 : 4,9-디메틸렌-2,7-디(티오펜-2-일)-1,6-디옥세케인의 합성Example 13: Synthesis of 4,9-dimethylene-2,7-di (thiophen-2-yl) -1,6-dioxane

Figure 112009036319410-pat00017
Figure 112009036319410-pat00017

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.485 mmol, 2-티오펜카바알데하이드 0.485 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.485 mmol을 사용하여 45% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.485 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.485 mmol of 2-thiophencarbaaldehyde, and trimethylsalyltriplate ( TMSOTf) 0.485 mmol gave the title compound in 45% yield.

오일; 1H NMR (400 MHz, CDCl3) δ 7.27 (d, 2H, J = 4.8 Hz), 7.01 (m, 4H), 5.24 (t, 2H, J = 7.2 Hz), 5.07 (m, 2H), 4.98 (m, 2H), 4.56 (d, 2H, J =12.8 Hz), 4.40 (d, 2H, J = 12.0 Hz), 2.98 (m, 2H), 2.74 (m, 2H); 13C NMR (100 MHz, CDCl3) δ 147.23, 145.16, 126.63, 124.96, 124.43, 104.86, 76.98, 70.95, 41.18; IR (thin film) 2935, 2850, 1645, 1261, 1037 cm-1 oil; 1 H NMR (400 MHz, CDCl 3 ) δ 7.27 (d, 2H, J = 4.8 Hz), 7.01 (m, 4H), 5.24 (t, 2H, J = 7.2 Hz), 5.07 (m, 2H), 4.98 (m, 2H), 4.56 (d, 2H, J = 12.8 Hz), 4.40 (d, 2H, J = 12.0 Hz), 2.98 (m, 2H), 2.74 (m, 2H); 13 C NMR (100 MHz, CDCl 3 ) δ 147.23, 145.16, 126.63, 124.96, 124.43, 104.86, 76.98, 70.95, 41.18; IR (thin film) 2935, 2850, 1645, 1261, 1037 cm -1

실시예 14 : 2,7-디(퓨란-3-일)-4,9-디메틸렌-1,6-디옥세케인의 합성Example 14 Synthesis of 2,7-di (furan-3-yl) -4,9-dimethylene-1,6-dioxane

Figure 112009036319410-pat00018
Figure 112009036319410-pat00018

상기 실시예 1과 같은 방법으로 실시하되, 2-((트리메틸실릴)메틸)부타-2,3-디엔-1-올 0.485 mmol, 3-퓨란카바알데하이드 0.485 mmol, 및 트라이메틸살릴트리플레이트 (TMSOTf) 0.485 mmol을 사용하여 26% 수율로 순수한 표제화합물을 얻었다. In the same manner as in Example 1, except that 0.485 mmol of 2-((trimethylsilyl) methyl) buta-2,3-diene-1-ol, 0.485 mmol of 3-furancarbaaldehyde, and trimethylsalyltriplate (TMSOTf 0.485 mmol was used to give the pure title compound in 26% yield.

m.p. 210-211 ℃; 1H NMR (400 MHz, CDCl3) δ 7.43 (d, 4H, J = 14.4 Hz ), 6.44 (s, 2H ), 5.23 (dd, 2H, J = 12.0, 3.6 Hz ), 5.18(s, 2H), 4.96 (s, 2H ), 4.17 (d, 2H, J = 12.4 Hz ), 3.90 (d, 2H, J = 12.4 Hz), 2.74 (t, 2H, J = 12.4 Hz ), 2.44 (d, 2H, J = 12.4 Hz ); 13C NMR (100 MHz, CDCl3) δ 143.50, 141.52, 140.37, 125.96, 120.32, 108.59, 71.53, 66.70, 45.24; IR (thin film) 3118, 2935, 1648, 1087, 1021 cm-1 mp 210-211 ° C; 1 H NMR (400 MHz, CDCl 3 ) δ 7.43 (d, 4H, J = 14.4 Hz), 6.44 (s, 2H), 5.23 (dd, 2H, J = 12.0, 3.6 Hz), 5.18 (s, 2H) , 4.96 (s, 2H), 4.17 (d, 2H, J = 12.4 Hz), 3.90 (d, 2H, J = 12.4 Hz), 2.74 (t, 2H, J = 12.4 Hz), 2.44 (d, 2H, J = 12.4 Hz); 13 C NMR (100 MHz, CDCl 3 ) δ 143.50, 141.52, 140.37, 125.96, 120.32, 108.59, 71.53, 66.70, 45.24; IR (thin film) 3118, 2935, 1648, 1087, 1021 cm -1

본 발명에 따른 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물은 천연물이나 신약의 중간체로서 유용하다. 1,6-dioxane compound represented by the formula (1) according to the present invention is useful as an intermediate of natural products or new drugs.

또한, 상기 화학식 1로 표시되는 1,6-디옥세케인 화합물은 엑소메틸렌 그룹을 이용한 디엘스-올더(Diels-Alder) 반응을 통해 또 다른 고리를 확장시켜, 정밀화학분야에서 매우 중요한 10각형 헤테로고리를 포함하는 다중고리 화합물 제조를 위한 중간체로 유용하다.In addition, the 1,6-dioxane compound represented by Chemical Formula 1 expands another ring through a Diels-Alder reaction using an exomethylene group, and is a pentagonal hetero which is very important in the field of fine chemicals. It is useful as an intermediate for the preparation of multicyclic compounds containing rings.

Claims (7)

하기 화학식 1로 표시되는 1,6-디옥세케인 화합물 :1,6-dioxane compound represented by the following formula (1): [화학식 1][Formula 1]
Figure 112009036319410-pat00019
Figure 112009036319410-pat00019
 상기 화학식 1에서, R은 탄소수 5 내지 15의 아릴기, 또는 질소, 산소 및 황 원자 중에서 선택된 헤테로원자가 1 내지 3개 포함된 탄소수 5 내지 15의 헤테로아릴기를 나타내며; n은 0 또는 1을 나타낸다.In Formula 1, R represents an aryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 15 carbon atoms containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms; n represents 0 or 1. 제 1 항에 있어서, The method of claim 1, R은 페닐기; 할로, 탄소수 1 내지 6의 알킬, 및 탄소수 1 내지 6의 알콕시 중에서 선택된 치환기가 1 내지 3개 치환된 페닐기; 티오펜일기; 또는 퓨란일기를 나타내고; n은 0 또는 1을 나타내는 것을 특징으로 하는 1,6-디옥세케인 화합물.R is a phenyl group; A phenyl group having 1 to 3 substituents selected from halo, alkyl having 1 to 6 carbon atoms, and alkoxy having 1 to 6 carbon atoms; Thiophenyl group; Or furanyl group; n represents 0 or 1, The 1, 6- dioxane compound. 제 1 항에 있어서, The method of claim 1, 3,4,8,9-테트라메틸렌-2,7-다이페닐-1,6-디옥세케인,3,4,8,9-tetramethylene-2,7-diphenyl-1,6-dioxane, 2,7-비스(4-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인,2,7-bis (4-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 2,7-비스(2-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인,2,7-bis (2-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 2,7-비스(3-디메톡시페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인,2,7-bis (3-dimethoxyphenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 3,4,8,9-테트라메틸렌-2,7-디-파라-톨일-1,6-디옥세케인,3,4,8,9-tetramethylene-2,7-di-para-tolyl-1,6-dioxane, 2,7-비스(4-플로로페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인,2,7-bis (4-fluorophenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 2,7-비스(4-클로로페닐)-3,4,8,9-테트라메틸렌-1,6-디옥세케인,2,7-bis (4-chlorophenyl) -3,4,8,9-tetramethylene-1,6-dioxane, 3,4,8,9-테트라메틸렌-2,7-디(티오펜-2-일)-1,6-디옥세케인,3,4,8,9-tetramethylene-2,7-di (thiophen-2-yl) -1,6-dioxane, 4,9-디메틸렌-2,7-디페닐-1,6-디옥세케인,4,9-dimethylene-2,7-diphenyl-1,6-dioxane, 2,7-비스(2-메톡시페닐)-4,9-디메틸렌-1,6-디옥세케인,2,7-bis (2-methoxyphenyl) -4,9-dimethylene-1,6-dioxane, 4,9-디메틸렌-2,7-디(메타-톨일)-1,6-디옥세케인,4,9-dimethylene-2,7-di (meth-tolyl) -1,6-dioxane, 2,7-비스(4-플로로페닐)-4,9-디메틸렌-1,6-디옥세케인,2,7-bis (4-fluorophenyl) -4,9-dimethylene-1,6-dioxane, 4,9-디메틸렌-2,7-디(티오펜-2-일)-1,6-디옥세케인, 또는4,9-dimethylene-2,7-di (thiophen-2-yl) -1,6-dioxane, or 2,7-디(퓨란-3-일)-4,9-디메틸렌-1,6-디옥세케인2,7-di (furan-3-yl) -4,9-dimethylene-1,6-dioxane 중에서 선택된 것을 특징으로 하는 1,6-디옥세케인 화합물.1,6-dioxane compound, characterized in that selected from. 하기 화학식 2로 표시되는 알코올 화합물과 하기 화학식 3으로 표시되는 알데하이드 화합물을 프린스 고리화 반응을 수행하여 제조하는 것을 특징으로 하는 하기 화학식 1로 표시되는 1,6-디옥세케인 화합물의 제조방법 :Method for producing a 1,6-diocecaine compound represented by the following formula (1) characterized in that the alcohol compound represented by the formula (2) and the aldehyde compound represented by the formula (3) by performing a Prince cyclization reaction:
Figure 112009036319410-pat00020
Figure 112009036319410-pat00020
 상기 반응식에서, R은 탄소수 5 내지 15의 아릴기, 또는 질소, 산소 및 황 원자 중에서 선택된 헤테로원자가 1 내지 3개 포함된 탄소수 5 내지 15의 헤테로아릴기를 나타내며; n은 0 또는 1을 나타낸다.In the above scheme, R represents an aryl group having 5 to 15 carbon atoms or a heteroaryl group having 5 to 15 carbon atoms containing 1 to 3 heteroatoms selected from nitrogen, oxygen, and sulfur atoms; n represents 0 or 1. 제 4 항에 있어서, The method of claim 4, wherein 상기 화학식 2로 표시되는 알코올 화합물을 기준으로, 트리메틸실릴 트리플루오로메탄설포네이트(TMSOTf)의 루이스산을 0.1 내지 2 당량 범위로 사용하는 것을 특징으로 하는 제조방법.Based on the alcohol compound represented by the formula (2), the production method characterized in that the Lewis acid of trimethylsilyl trifluoromethanesulfonate (TMSOTf) is used in the range of 0.1 to 2 equivalents. 제 4 항에 있어서, The method of claim 4, wherein 상기 프린스 반응용매로는 테트라하이드퓨란을 사용하는 것을 특징으로 하는 제조방법.The prince reaction solvent is characterized in that for using tetrahydrofuran. 제 4 항에 있어서, The method of claim 4, wherein 상기 프린스 반응온도는 -78 ℃ 내지 30 ℃ 범위인 것을 특징으로 하는 제조방법.The prince reaction temperature is characterized in that the production method ranges from -78 ℃ to 30 ℃.
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