• 약학회지
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• 제56권6호
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• pp.390-394
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• 2012

A series of new pyridazinyl sulfoxides 3a~e and pyridazinyl sulfones 4a were synthesized for development of candidates to retain anticancer activity. The utility of sulfoxides and sulfones in both laboratory and industrial practice was quickly recognized, and these species have been extensively utilized, including as pharmaceutical intermediates and anticancer agents. Alkylthiopyridazines 2a~e were prepared from the 3,6-dichloropyridazine using allylthiolation with alkyl mercaptan. Sulfides could be oxidized to sulfoxides or sulfones using 1~3 equivalents of hydrogen peroxide as an oxidant. The oxidation of sulfoxides to sulfones was also accomplished with aqueous hydrogen peroxide. Formation of 3a~e and 4a was undertaken with stirring using 35% hydrogen peroxide at room temperature in acetic acid for 18~72 h. Synthetic compounds were identified using NMR spectrum.

• Bulletin of the Korean Chemical Society
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• 제30권9호
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• pp.1927-1928
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• 2009

• Bulletin of the Korean Chemical Society
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• 제28권2호
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• pp.171-172
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• 2007

• 대한화학회지
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• 제33권2호
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• pp.247-256
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• 1989

4-아세틸-5,6-디히드로-2-메틸-1,4-티아진-3-카르복실산 유도체 24를 상응하는 티아졸리딘 술폭시드의 고리확대에 의하여 제조하였다. 2-메틸-1,3-티아졸라딘-2-아세트산 유도체 12를 산화하여 시스와 트랜스 술폭시드, 14 및 15를 얻었으며 이들의 구조는 수소핵자기 공명스펙트럼, 적외선 흡수스펙트럼, 그리고 중수소 치환반응에 의한 regioselectivity에 근거하여 결정하였다. 산촉매 존재하에서 시스와트랜스 술폭시드, 14 및 15는 중간체 술페닌산 18을 거쳐 디히드로-1,4-티아진 24로 전환되었다. 그러나 중성조건($100^{\circ}C$의 DMF)에서 트랜스 술폭시드 15는 중간체 술페닌산 21을 거쳐 isomeric 디히드로-1,4-티아진 27로 전환하였다. 화합물 24와 27의 생성반응기전도 논의하였다.

• Bulletin of the Korean Chemical Society
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• 제27권1호
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• pp.106-110
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• 2006

Photocatalytic electron transfer reactions of aryl benzyl sulfides using 2,4,6 triphenylpyrilium tetrafluoroborate ($TP^+BF_4^-$) resulted in the oxidation of these sulfides to the corresponding sulfoxides and also in most cases in the C-S bond cleavage of them along with formation of aromatic aldehydes. In these reactions, the formation of sulfide radical cation has been proposed, which undergoes either oxidation to the corresponding sulfoxide or C-S bond cleavage to the formation of aromatic aldehydes. The further oxidation of sulfoxides to sulfones has not been observed. The influence of substrate structures on the reaction pathways as well as the role of $O_2$ in this respect is discussed.

• Bulletin of the Korean Chemical Society
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• 제25권9호
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• pp.1379-1384
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• 2004

Rearrangements of 1,3-oxathiolane sulfoxides 8 and 9 in the presence of base are described from a mechanistic viewpoint of sigmatropic and elimination reactions. In the presence of triethylamine the (Z)-sulfoxide 8 gave the corresponding thiolsulfinate 10 by way of dimerization of the sulfenic acid intermediate 2 at room temperature while the (E)-sulfoxide 9 was recovered even after refluxing in ethyl acetate by the reversal of the [2,3]-sigmatropic rearrangement of the sulfenic acid 4. Triethylamine promoted the developing charge separation in the transition state of the sigmatropic rearrangement of the (Z)-sulfoxide 8 to facilitate the ring opening to the sulfenic acid 2. The reason for more facile ring opening of the (Z)-sulfoxide 8 in comparison with the corresponding (E)-sulfoxide 9 is attributable to the differences in the reactivity of the hydrogen adjacent to the carbonyl group. Triethylamine was not strong base to deprotonate the carbonyl-activated methylene hydrogen of the (E)-sulfoxide 9 but enough to catalyze the sigmatropic process of the sulfoxides. The sulfenic acid 2 dimerized to the thiolsulfinate 10 while the sulfenic acid 4 proceeded the sigmatropic ring closure. In the presence of strong base such as potassium hydroxide, the elimination reaction was predominant over the sigmatropic rearrangement. In this reaction condition, both sulfoxides 8a and 9a gave a mixture of the disulfide 12, the isomeric disulfide 14, and the sulfinic acid 13. Under the strong alkaline condition an elimination of activated hydrogen from the carbon adjacent to the carbonyl group to furnish the sulfenic acid 2a and the isomeric sulfenic acid 18. The formation of the transient intermediate in the reaction was proven by isolation of the isomeric disulfide 14. The reactive entity was regarded as the sulfenic acid rather than sulfenate anion under these reaction conditions.

• 대한화학회지
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• 제37권1호
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• pp.119-130
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• 1993

한 분자 내에 3개의 chiral 중심이 있는 1,3-티아졸리딘 술록시드 1의 입체화학을 중수소치환반응 및 trapping 반응을 통해 밝혔다. 3-아세틸-1,3-티아졸리딘 5의 부분이성질체를 분리한 다음 6과 8을 각각 술록시드로 산화시켜 상응하는 $\alpha$-시스 10, $\alpha$-트랜스 11과 $\beta$ -시스 12, $\beta$ -트랜스이성체 13을 얻었다. 술폭시드 10은 중성 조건하의 환류하는 벤젠 또는 톨루엔 용액 중에서 열역학적으로 보다 안정한 13으로 이성질화하였다. 중수소치환반응에 의해서 술폭시드 13과 술폭시드 11의 2-메틸기의 수소원자는 중수소로 치환되었다. 술폭시드 10과 12로부터 sigmatropic 전위에 의해서 생성된 중간체 슬페닌산 25 및 26은 2-머캡토벤조티아졸(2-MBT)에 의하여 trap되어 디술피드 27 및 28로 전환되었으나 동일한 반응조건하에서 술폭시드 11 및 13은 환팽창 생성물 디히드로-1,4-티아진 29로 전환되었다. 산촉매 존재하에서 술폭시드 10, 11, 12는 술폭시드 13을 통해서 디히드로-1,4-티아진 29로 정량적으로 전환되었다. 술폭시드들의 이성질화 및 29의 생성메카니즘도 기술하였다.

• Bulletin of the Korean Chemical Society
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• 제17권1호
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• pp.4-5
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• 1996

• Bulletin of the Korean Chemical Society
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• 제29권7호
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• pp.1332-1334
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• 2008

Stable crystalline 1-Benzyl-4-aza-1-azonia-bicyclo[2.2.2]octane tribromide (BABOT), can be readily synthesized from the reaction of the corresponding bromide with $HNO_3$ and aqueous KBr. Selective Oxidation of a variety of dialkyl and alkyl Aryl sulfides to the corresponding sulfoxides in high yield was achieved by this reagent in solution ($CH_3CN/H_2O$) and solvent free conditions. The reaction proceeds under neutral and mild conditions and can be carried out easily at room temperature with regeneration of BABOT. In this method purification of products is straightforward and no over oxidation to sulfone was noted.

• Bulletin of the Korean Chemical Society
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• 제8권3호
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• pp.219-219
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• 1987