시안화물을 사용하지 않는 Thiocyanates 와 Cyanamides의 실용적인 합성 방법

다국어 초록 (Multilingual Abstract)

In Chapter 1, we summarized methods for the synthesis of cyanides. Many researchers are developing electrophilic cyanide transfer reagents with various electronic properties to replace the use of highly toxic and unstable cyanogen halides (BrCN, ClCN). These reagents offer advantages such as broad substrate scope, high reactivity, and the ability to synthesize cyanides under generally mild conditions. However, the synthesis of most of these reagents still relies on cyanogen halides (BrCN, ClCN), and many of them also exhibit toxicity. Therefore, further research is needed to eliminate the reliance on hazardous cyanogen halides (BrCN, ClCN).
In Chapter 2, we delineated the entire process involved in developing a novel method for thiocyanates and cyanamides. We developed a synthesis method for thiocyanates (SCN) and cyanamides (NCN) without using hazardous cyanogen halides. A total of 28 examples were reported, and N-hydroxy-2-oxopropanimidoyl chloride 1 was identified as an efficient potential cyanating reagent. It is easy to handle, enables large-scale synthesis, and offers simple operational procedures. Two types of nucleophiles, thiols and secondary amines, were applicable, whereas substrates with lower nucleophilicity, such as oxygen, did not undergo conversion. Thiocyanates were synthesized via a one-pot reaction, while cyanamides required a two-step process. Additionally, using our method, we successfully synthesized known cyanating reagents, 1-cyanobenzotriazole 9 and 1,3-dioxoisoindoline-2-carbonitrile 11, with good yields and on a large scale, avoiding the use of cyanogen halides previously required. Furthermore, we synthesized N-cyanopyrazole 13 for the first time and reported its NMR, IR spectra, and mass data.

목차 (Table of Contents)

• Chapter Ⅰ. Cyanides 합성을 위한 연구에 대한 소개 1
• 1. 연구배경 1
• 2. 질소 기반 친전자성 사이안화 시약 2
• 2.1 N-cyano-N-phenyl-p-methylbenzenesulfonamide (NCTS) 2
• 2.2 1-Cyanobenzotriazole(BtCN) 3
• 2.3 2-Cyanopyridazin-3(2H)-ones 4
• 2.4 2-cyanoisothiazolidine 1,1-dioxide (NCITD) 5
• 3. 황 기반 친전자성 사이안화 시약 6
• 3.1 5-(cyano)dibenzothiophenium salt 6
• 3.2 p-Toluenesulfonyl cyanide (TsCN) 7
• 4. 아이오딘 기반 친전자성 사이안화 시약 8
• 4.1 Cyanobenziodoxols(CBX, CDBX) 8
• 4.2 3,5-di(trifluoromethyl)phenyl(cyano)iodonium triflate (DFCT) 9
• 5. 결론 10
• 6. 참고문헌. 11
• Chapter Ⅱ. 시안화물을 사용하지 않는 Thiocyanates 와 Cyanamides의 실용적인 합성 방법 12
• 1. 연구 가설 12
• 2. 결과 및 고찰 14
• 2.1 Cyanides 합성 준비 : N-hydroxy-2-oxopropanimidoyl chloride 1 합성 14
• 2.2 반응 최적화 15
• 2.3 Thiocyanates (SCN) 합성 18
• 2.4 Cyanamides 합성 19
• 2.5 합성 유용성 : 알려진 친전자성 사이안화 시약 합성 23
• 3. 결론 25
• 4. 실험 26
• 4.1 General 26
• 4.2 N-hydroxy-2-oxopropanimidoyl chloride 1 합성 방법 27
• 4.3 Thiocyanates (6a–6n) 일반적인 합성 방법 28
• 4.4 중간체 5 일반적인 합성 방법 32
• 4.5 Cyanamide 7 일반적인 합성 방법 36
• 4.6 1-c yanobenzotriazole 9 합성 방법 39
• 4.7 1,3-dioxoisoindoline-2-carbonitrile 11 합성 방법 40
• 4.8 N-cyanopyrazole 13 합성 방법 41
• 5. 1H-NMR, 13C-NMR, 19F-NMR 43
• 6. 참고문헌 75
• 영문요약 76