우리는 국립 과학 재단 (National Science Foundation) (CHE0910597)과이 작품을 지원하기위한 국립 보건원 (P50-GM067982)을 감사드립니다. 우리는 형광 측정에 관한 도움을 토론 교수 마이클 Trakselis (피츠버그 대학)에 감사하고 있습니다. 우리는 형광 데이터를 수집에서의 도움 크리스티 Gogick과 로빈 슬로안을 (피츠버그 대학) 인정합니다.

1. 전자 레인지를 이용한 Dehydrogenative DA 반응 <ol><li> 파라 - 클로로 스티렌 유도체 (0.045 g, 0.18 mmol)과 0.060 M 솔루션을 생성 할 저어 바 장착 2-5 ML의 전자 방사선 유리 병에 (3 ML) 1,2-dichloroethane을 추가합니다. 높은 농도 원치 않는 제품의 형성으로 이어질 있기 때문에 집중이 사용됩니다. </li><li> 전자 레인지의 방사선 약병 뚜껑 및 전자 합성기 공동에 배치합니다. </li><li> 감동과 및 고정 대기 시간에 200 분 동안 180 ° C에서 솔루션을 비추다. 보류 시간은 조사가 지정된 온도에서 발생합니다 얼마나 오래입니다. 반응 혼합물은 색 금색으로 바뀝니다. 긴 반응 시간은 반응의 수율에 해로운되지 않습니다. </li><li> 반응이 eluent로 아세테이트 / 헥산 에틸 5 %를 채용 얇은 층 크로마토 그래피 (T​​LC)에 의한 완료 확인합니다. UV 빛과 칼륨 과망간산 염 얼룩과 TLC 판을 표시합니다. reactan의 R F 조t와 제품은 각각 0.2 및 0.25입니다. </li><li> 전자 레인지의 반응 약병을 씻어하기 위해 1,2-dichloroethane의 1 ML을 사용하여 섬광 유리 병에 반응을 전송합니다. 섬광 병에 솔루션의 약 3 ML에있는이 발생합니다. </li><li> 40 감소 된 압력에서 섬광 유리 병의 내용을 집중 ° C 회전 증발기 (10-30 mmHg)를 사용하여. 용매의 증발 5-10 분, 45 원유 갈색 기름 MG 얻을 수 있어야합니다. 원유는 안정적이며, 분해하지 않고 무한정 저장할 수 있습니다. </li><li> 흰색 고체로 나프탈렌 41 밀리그램을 취득 할 수 eluent로 아세테이트 / hexanes 에틸 5퍼센트와 실리카 겔의 피펫을 통해 여과하여 원유를 정화. </li><li> 용매로 진정제를 맞았을 클로로포름 (CDCl 3)를 사용하여 1 H 핵 자기 공명 (NMR) 분광법하여 제품의 신원을 확인합니다. 다음과 같이 300 MHz의 NMR 분광계를 들어, 나프탈렌의 1 H NMR 스펙트럼은 다음과 같습니다 : 7.80 (D, J = 1.8 Hz에서, 1H), 7.72 (D, J = 9.0 Hz에서, 1H), 7.70 (S, 1H), 7.38 (DD, J = 1.8, 9.0 Hz에서, 1H), 3.07 (t, J = 7.1 Hz에서 , 4H), 2.66 (S, 3H), 2.18 (P, J = 7.1 Hz에서, 2H) PPM. </li></ol> 2. Buchwald-Hartwig 팔라듐 (Palladium) - 촉매 크로스 커플 링 반응 <ol><li> 저어 바, 캡 약병을 갖춘 오븐 건조 0.5-2 ML의 Biotage의 전자 방사선 유리 병에 RuPhos palladacycle (3 MG, 0.004 mmol)를 추가합니다. </li><li> 작은 게이지 바늘과 캡의 심장을 피어싱하여 질소를 세 번으로 병을 벗어나 충전. 병을 정화하는 것은 완료되면, 바늘을 제거합니다. 전자 방사선 유리 병은 반응 동안 밀폐 된 튜브 역할을하며, 최소한의 공기가 반응 용기에 존재 할 때 최상의 결과를 얻을 수 있습니다. </li><li> 심장을 통해 감동과 주사기를 통해 리튬 비스 (trimethylsilyl) 아미드 (THF, 0.32 mmol의 1.0 M 솔루션의 0.32 ML)을 추가합니다. 이 솔루션은 빨간색으로 켜집니다. </li><li> 2-10 분 동안 교반 한 후, (0.038 g, 나프탈렌을 추가주사기를 통해 0.3 ML 무수 tetrahydrofuran (THF)에 0.16 mmol). 추가 THF는 (최대 0.2 ML) 완전히 나프탈렌을 분해하는 데 사용할 수 있습니다. </li><li> 감동의 2-10 분 후, 주사기를 통해 dimethylamine을 (THF, 0.24 mmol의 2.0 M 솔루션의 0.12 ML) 추가하고 preheated 85 ° C 오일 목욕에 반응 용기를 낮추십시오. </li><li> 반응이 TLC에 의해 완료 ° C, 또는 때까지 85 3 시간 동안 반응 혼합물을 가열. 반응 혼합물은 색 진한 갈색이 될 것입니다. TLC를 들어, 아세테이트 / eluent로 hexanes 에틸 20 %를 사용하고, UV 빛과 칼륨 과망간산 염 얼룩으로 인한 판을 표시합니다. 반응물과 제품의 R의 F는 각각 0.5 0.4입니다. </li><li> 실내 온도에 반응을 냉각, 유리 병 캡을 제거하고 포화 수성 염화 암모늄 용액과 반​​응 (10 ML)를 잃게. </li><li> 60 ML 분리 깔때기 사용하여 유기 층에서 수성 레이어를 분리합니다. 에틸 아세테이트와 수성 층을 세 번 압축을 풉니 다 (12 ML). </li><li> 분리 깔때기에 유기 레이어를 결합하고 염수 (15 ML)로 한 번 씻는다. </li><li> 10 분에 나트륨 황산을 통해 결합 된 유기 층을 건조하고 중력 여과하여 나트륨 황산을 제거합니다. </li><li> 회전 증발기를 사용, 30 ° C (10-30 mmHg)에서 감소 된 압력에 따라 결과 솔루션을 집중. 용매의 증발 5-10 분을 필요로하고, 원유 갈색 기름이 취득됩니다. </li><li> 아세테이트 / eluent로 hexanes 에틸 1.5 cm 크로마토 그래피 컬럼 및 5 %를 실리카 겔 칼럼 크로마토 그래피에 의한 원유 제품을 정화. 염료는 노란색 고체의 27 밀리그램으로 얻을 수 있습니다. </li><li> 1 H NMR 분광법은 용매로 CDCl 3을 사용하여 제품의 신원을 확인합니다. 400 MHz의 NMR 분광계, 염료은 다음과 위해 할 수있는 일 H NMR 스펙트럼의 경우 : 7.64 (D, J = 9.0 Hz에서, 1H), 7.56 (S, 1H), 7.11 (DD, J = 2.5, 9.0 Hz에서, 상반기 ), 6.87 (D, J = 2.5 Hz에서, 1H), 3.02 (S, 6H), 3.02-2.87 (m, 4H), 2.65 (S, 3H), 2.12 (P, J = 7.3 Hz에서, 2H) PPM. </li></ol> 3. Photophysical 연구 염료 솔루션의 준비 <ol><li> 깨끗하고 마른 10 ML의 용적 플라스크에 염료의 1 밀리그램을 송금 염료의 0.4 × 10 -3 M 주식 솔루션을 얻기 위해 dichloromethane과 볼륨 (DCM)로 희석. </li><li> 두 번째 열 ML 용적 플라스크에 재고 솔루션 253 μl를 전송하고 염료의 1 × 10 -5 M 솔루션을 준비하는 DCM이있는 볼륨에 희석. 이 솔루션은 UV-VIS와 염료의 형광 데이터를 모두 수집하는 데 사용됩니다. </li></ol> 4. UV-표시 흡수 분광 <ol><li> DCM으로 두 석영 분광 광도계의 셀을 입력합니다. 이러한 빈 샘플입니다. UV-VIS 분광 광도계의 구멍으로 넣으십시오. 셀의 광학 표면을 만지지 마십시오. 광학 축에 직면하지 않는 측면 플레이트의 상단에있는 셀을 처리합니다. </li><li> 로 수단 매개 변수를 설정2 슬릿 폭과 480 nm의 / 분의 수집 속도. 샘플의 이름을 선택하고 600에서 200 나노 미터에 수집 범위를 선택합니다. </li><li> 배경 스펙트럼을 수집, 악기에서 샘플 셀을 제거를 비우하고, 충전 전에 1 × 10 -5 M 염료 솔루션의 여러 부분을 씻어. 셀을 overfilling하지 마십시오. 홀더에 샘플 셀을 다시 삽입하기 전에 조심스럽게 깨끗한 렌즈 조직과 세포 창을 닦으십시오. </li><li> 샘플의 흡수 스펙트럼을 수집합니다. 흡수 최대 377 나노 미터에서 관찰된다. </li><li> 다른 샘플에 UV-VIS 흡수 분석을 실행하기 전에 물, 아세톤 및 에탄올과 석영 분광 광도계 세포를 조심스럽게 닦아주십시오. </li><li> 수집 된 데이터를 짜고 분석 Excel 또는 원산지 소프트웨어를 사용합니다. </li></ol> 5. 형광 발광 분석법 <ol><li> 1 × 10 -5 M의 염료 솔루션 석영 fluorometer 셀을 입력 spectrofluoromet에 배치어. 세포의 광학 표면과 피부 접촉을 피하십시오. </li><li> 수단 매개 변수를 설정합니다 : 334 nm의에서 여기 파장, 2 슬릿 폭, 0.1 nm의 / 초의 수집 속도, 390-750 nm의에서 수집 범위를. 390 나노 미터 컷 -의 필터는 방출 소스에서 분산 된 광을 제거 할 필요합니다. </li><li> 샘플의 형광 방출 스펙트럼을 수집합니다. 형광 방출 최대 510 나노 미터에서 관찰된다. </li><li> 다른 샘플에 형광 분석을 실행하기 전에 석영 fluorometer 물이있는 셀, 아세톤 및 에탄올를 청소합니다. </li><li> 수집 된 데이터를 짜고 분석 Excel 또는 원산지 소프트웨어를 사용합니다. </li></ol>

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Soc. 134 (30), 12418-12421 (2012).</li><li>OriginLab Corporation. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Origin 8 User Guide. , (2007).</li></ol>

제작자들은 더 경쟁 금융 이익이 없다는 점 선언합니다.

전자 레인지 - 지원 Dehydrogenative DA 반응 전자 조사에 의한 styrenyl 전구체의 분자 dehydrogenative DA 반응 (MWI)은 최소 30 분 (그림 1) 18을 필요로 71-100% 높은 수율과 짧은 반응 시간에 다양한 나프탈렌 구조를 생산하고 있습니다. dehydrogenative DA 반응을 수행하는 가장 어려운 점은 용매 특성을 다양한 최적의 난방을 보장하기 위해 고려해야 할 필요가 있기 때문에 종?...

작은 분자 설계 및 합성 의약품, 살충제, 유기 염료, 1 많은이 포함되어 과학 분야의 범위의 개발에 중요합니다. Diels-앨더 (DA)와 dehydro-Diels-앨더 (DDA) 반응은 작은 고리과 아로마 화합물 2-4 합성 특히 강력한 도구입니다. 또한, alkyne dienophiles과 스티렌 dienes의 열 dehydrogenative DA 반응은 처음에 더 산화 조건 5에서 aromatize 수 있습니다 cycloadducts을 형성하여 방향족 화합물의 합성에 잠재적으로 유익한 경로를 제공합니다. alkynes과 스티렌 dienes의 열 분자 dehydrogenative DA 반응을 채용함으로써, 문제가 일반적으로 바람직하지 않은 [2 + 2] cycloaddition 5,6 및 중합 반응 7 가난한 regioselectivity, 완화하고 나프탈렌 화합물로 디엔로 활용 스티렌과 관련된 생성 할 수 있습니다. alkynes와 styrenes의 열 분자 dehydrogenative DA 반응은 상당한 문제없이되지 않습니다. 첫째, 대부분의 반응은 낮은 수율, 긴 반응 시간, 높은 반응 온도 8-11로 고통 받고 있습니다. 또한 많은 반응은 나프탈렌 제품의 독점 형성을 촉진하지 않는, 나프탈렌과 dihydronaphthalene 모두 생산, 종종 칼럼 크로마토 그래피 11,12에 의해 분리 혼합물로. 전구체 스티렌 - ynes의 tethers은 이종 원자 및 / 또는 카르 보닐 moieties을 포함하도록 제한됩니다. 하나의 예제는 250 조건을 필요로 모든 탄소 함유 테 더링에 대해보고하고 있습니다 ° C 나프탈렌 형성 (10) 얻기 위해 48 시간을위한 스트레이트로. 시작 물질의 tethers 내에서 제한된 다양한 또한이 방법의 가장 심각한 제약 중 하나는 종래의 온도 조건 하에서 용납 기능이 없다는 것입니다.출발 물질의 alkyne 터미널이 중 unsubstituted 또는 페닐 또는 trimethylsilyl (TMS) 잔기 8-13으로 추가됩니다. 하나의 인스턴스에서, alkyne 터미널에서 에스테르는 dehydrogenative DA 반응을 받게 표시하지만, 나프탈렌과 dihydronaphthalene 제품 (11)의 혼합이 발생합니다.합니다 나중에 제안 alkyne 말단에 추가 TMS 그룹은 높은 수율 10 전용 나프탈렌 형성을 달성 할 필요가 있습니다 것을 제안합니다. 열 dehydrogenative DA 반응에 대해보고 다양한 기능의 결핍은 심각한 독특한 나프탈렌 구조의 조립 방향이 반응의 가능성을 제한합니다. 나프탈렌 구조의 변화에 대한 열망은 여러 과학 분야, 특히 유기 형광 염료 14,15의 작은 분자 빌딩 블록으로서의 기능 때문이다. 작은 ORG의 우수한 공간 해상도와 반응 시간실시간 이벤트 (16)을 모니터링하기위한 anic 염료는 상업적으로 이용 가능한 형광 화합물의 수백의 개발하게되었다. 이 염료의 대부분은 개별 photophysical 및 화학 특성 15 naphthalenes 있습니다. 개별 기능을 모니터링 할 특정 특성을 가진 형광 염료를 선택하면 더욱 다양한 photophysical 특성을 가진 fluorophores의 새로운 클래스에 대한 증가 필요로 연결하는 도전입니다. 이를 위해 독특한 나프탈렌 골격의 다양 화를 허용 alkynes와 styrenes의 열 분자 dehydrogenative DA 반응은 새로운 나프탈렌 함유 형광 염료를 개발하는 응용 프로그램과 잠재적으로 도움이 될 것입니다. 이 높은 화학 수율로 연결 화학 샘플의 더 균일 한 가열, 빠른 반응 속도, milder 반응 조건을 제공하기 때문에 기존 난방에 대한 대안으로, 전자 레인지를 이용한 화학이 바람직하다제품 17 초, 종종 다른 선택도. styrenes의 분자 dehydrogenative DA 반응에 전자 레인지를 이용한 대 종래의 가열 조건을 채용하면, 이전에 가난한 수율을 증가 분으로 일에서 반응 시간을 줄여 반응 온도를 낮추고, 더 많은 선택 형성을 제공하여이 방법론과 관련된 많은 문제를 제거하는 역할을 원하는 나프탈렌 제품의. 전자 레인지를 이용한 반응 조건은 이전에 얻기 어려운했던 나프탈렌 제품에 기능을 더 다양한 결합을 촉진 할 가능성이 높습니다 할 수 있습니다. 하나의 이전 예제는 나프탈렌과 dihydronaphthalene 모두 90 % 수율은 170 ° C 12 15 분 최소로 취득 된에 dehydrogenative DA 반응에 전자 레인지를 이용한 조건을 활용하여보고되었습니다. 여기에는 전자 레인지를 이용한 분자 dehydroge을보고최소 30 분 및 양적 수율로 높은 18 작용과 다양한 나프탈렌 제품의 독점 형성에 이르게 styrenyl 파생 상품의 기본 DA 반응. 이 프로토콜의 유틸리티는 더 인기있는 상용화 된 염료 Prodan 19 그런 경쟁 photophysical 특성을 가진 소설 solvatochromic 형광 염료로 나프탈렌 제품의 한 단계 변환에 의해 증명된다.

<table border="1">
	<tbody>
		<tr>
			<td>Reagent/Material</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>1,2-Dichloroethane, ACS reagent &ge;99.0%</td>
			<td>Sigma-Aldrich</td>
			<td>319929</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>SiliaPlate G TLC - glass-backed, 250 &mu;m</td>
			<td>Silicycle</td>
			<td>TLG-R10011B-323</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Ethyl acetate, certified ACS &ge;99.5%</td>
			<td>Fisher Scientific</td>
			<td>E14520</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Hexanes, certified ACS &ge;98.5%</td>
			<td>Fisher Scientific</td>
			<td>H29220</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Silica gel, standard grade</td>
			<td>Sorbent Technologies</td>
			<td>30930M</td>
			<td>60 A, 40-63 &mu;M (230 x 400 mesh)</td>
		</tr>
		<tr>
			<td>RuPhos palladacycle</td>
			<td>Strem</td>
			<td>46-0266</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Nitrogen gas</td>
			<td>Matheson TRIGAS</td>
			<td>NI304</td>
			<td>Nitrogen 304cf, industrial</td>
		</tr>
		<tr>
			<td>Lithium bis(trimethylsilyl) amide solution</td>
			<td>Sigma-Aldrich</td>
			<td>225770</td>
			<td>1.0 M solution in THF</td>
		</tr>
		<tr>
			<td>Tetrahydrofuran anhydrous &ge;99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>401757</td>
			<td>Inhibitor-free</td>
		</tr>
		<tr>
			<td>Dimethylamine solution</td>
			<td>Sigma-Aldrich</td>
			<td>391956</td>
			<td>2.0 M solution in THF</td>
		</tr>
		<tr>
			<td>Ammonium chloride</td>
			<td>Fisher Scientific</td>
			<td>A661-500</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Sodium sulfate, anhydrous (granular)</td>
			<td>Fisher Scientific</td>
			<td>S421-500</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Chromatography column</td>
			<td>Chemglass</td>
			<td>CG-1188-04</td>
			<td>&frac12; in ID x 18in E.L.</td>
		</tr>
		<tr>
			<td>Cyclohexane, &ge;99.0%</td>
			<td>Fisher Scientific</td>
			<td>C556-1</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Toluene anhydrous, 99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>24451</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>1,4-Dioxane anhydrous, 99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>296309</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Tetrahydrofuran anhydrous, &ge;99.9%</td>
			<td>Sigma-Aldrich</td>
			<td>186562</td>
			<td>250 ppm BHT as inhibitor</td>
		</tr>
		<tr>
			<td>Dichloromethane</td>
			<td>Sigma-Aldrich</td>
			<td>650463</td>
			<td>Chromasolv Plus</td>
		</tr>
		<tr>
			<td>Chloroform, &ge;99.8%</td>
			<td>Fisher Scientific</td>
			<td>C298-1</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Acetonitrile anhydrous, 99.8%</td>
			<td>Sigma-Aldrich</td>
			<td>271004</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Dimethyl sulfoxide, &ge;99.9%</td>
			<td>Fisher Scientific</td>
			<td>D128</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Ethyl alcohol</td>
			<td>Pharmco-AAPER</td>
			<td>11ACS200</td>
			<td>Absolute</td>
		</tr>
		<tr>
			<td>Equipment</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Synthesizer</td>
			<td>Biotage</td>
			<td>Biotage Initiator Exp</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Vial</td>
			<td>Biotage</td>
			<td>352016</td>
			<td>0.5 - 2 ml</td>
		</tr>
		<tr>
			<td>Microwave Vial</td>
			<td>Biotage</td>
			<td>351521</td>
			<td>2 - 5 ml</td>
		</tr>
		<tr>
			<td>Microwave Vial Cap</td>
			<td>Biotage</td>
			<td>352298</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Synthesizer</td>
			<td>Anton Paar</td>
			<td>Monowave 300</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Vial G4</td>
			<td>Anton Paar</td>
			<td>99135</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Microwave Vial Cap</td>
			<td>Anton Paar</td>
			<td>88882</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>NMR Spectrometer</td>
			<td>Bruker</td>
			<td>Avance</td>
			<td>300 or 400 MHz</td>
		</tr>
		<tr>
			<td>UV-Visible Spectrometer</td>
			<td>PerkinElmer</td>
			<td>Lamda 9</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Spectrophotometer cell</td>
			<td>Starna Cells</td>
			<td>29B-Q-10</td>
			<td>Spectrosil quartz, path length 10 mm, semi-micro, black wall</td>
		</tr>
		<tr>
			<td>Spectrofluorometer</td>
			<td>HORIBA Jobin Yvon</td>
			<td>FluoroMax-3 S4</td>
			<td>&nbsp;</td>
		</tr>
		<tr>
			<td>Fluorometer cell</td>
			<td>Starna Cells</td>
			<td>29F-Q-10</td>
			<td>Spectrosil quartz, path length 10 mm, semi-micro</td>
		</tr>
	</tbody>
</table>

microwave-assisted intramolecular dehydrogenative diels-alder reactions for the synthesis of functionalized naphthalenes/solvatochromic dyes

작용 naphthalenes 자연이나 생물학적 활성 분자의 합성에서 새로운 유기 염료의 준비에 이르기까지 다양한 연구 분야의 다양한 응용 프로그램을 수 있습니다. 다양한 전략 나프탈렌 공사장 공중 발판에 액세스 할보고되었습니다 있지만, 많은 절차가 계속 회전에서 사용할 기판의 범위를 좁혀 통합 기능의 측면에서 한계를 제시한다. 대체 naphthalenes에 직접 액세스 할 수 있도록 다양한 방법의 개발은 따라서 매우 바람직하다. Diels-앨더 (DA) cycloaddition 반응이 즉시 사용할 수 출발 물질의 포화 및 불포화 링 시스템의 형성을위한 강력하고 매력적인 방법입니다. styrenyl 파생 상품의 새로운 전자 레인지를 이용한 분자 dehydrogenative DA 반응이 여기에 작용 cyclopenta의 다양한 생성 설명 [B] 기존의 합성 방법을 사용하여 준비 할 수 없습니다 naphthaleness입니다. 기존 난방에 비해, 전자 조사는 반응 속도를 가속화 수율을 향상하고, 원치 않는 부산물의 형성을 제한합니다. 이 프로토콜의 유틸리티는 더 Buchwald-Hartwig 팔라듐 - 촉매 크로스 커플 링 반응을 통해 소설 solvatochromic 형광 염료로 DA의 cycloadduct의 전환에 의해 증명된다. 형광 분광법은 유익하고 중요한 분석 기술로, 환경 과학, 의학, 약학 및 세포 생물학 등의 연구 분야에서 핵심적인 역할을 담당하고 있습니다. 전자 레인지를 이용한 dehydrogenative DA 반응에 의해 제공하는 유기 fluorophores의 다양한 액세스는 이러한 분야에서 더 발전 할 수 있습니다.

180에서 styrenyl 파생 상품의 전자 조사 (MWI)가 완료 cyclopenta에서 ° C 결과 [B] 최소 30 분 및 양적 수율 (그림 1)에 높은 18 나프탈렌 형성. 더 dihydronaphthalene 부산물은 관찰되지 않습니다, 1 H NMR 분광법에 의해 제품이 방사선 조사 후 추가 정화 (그림 2)에 대한 필요없이 순수 나타납니다. 나프탈​​렌 프레임 워크에 다양한 변화도 테 더링으로 ?...

Watch this Scientific Journal Video about Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes at JoVE.com

Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

전자 레인지를 이용한 분자 dehydrogenative Diels-앨더 (DA) 반응 작용 cyclopenta에 간결한 액세스를 제공 [<em&gt; B</em&gt;] 나프탈렌의 빌딩 블록. 이 방법의 유틸리티는 Buchwald-Hartwig 팔라듐 - 촉매 크로스 커플 링 반응을 통해 소설 solvatochromic 형광 염료로 dehydrogenative DA의 cycloadducts 중 하나 단계 변환에 의해 증명된다.

작용 Naphthalenes / Solvatochromic의 염료의 합성을위한 전자 레인지를 이용한 분자 Dehydrogenative Diels-앨더 반응

Functionalized naphthalenes have applications in a variety of research fields ranging from the synthesis of natural or biologically active molecules to ...

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Dienes, Conjugated Pi Systems, and Pericyclic Reactions

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16.9K 조회수.  University of Pittsburgh. 전자 레인지를 이용한 분자 dehydrogenative Diels-앨더 (DA) 반응 작용 cyclopenta에 간결한 액세스를 제공 [ B] 나프탈렌의 빌딩 블록. 이 방법의 유틸리티는 Buchwald-Hartwig 팔라듐 - 촉매 크로스 커플 링 반응을 통해 소설 solvatochromic 형광 염료로 dehydrogenative DA의 cycloadducts 중 하나 단계 변환에 의해 증명된다.

비디오: Microwave-assisted Intramolecular Dehydrogenative Diels-Alder Reactions for the Synthesis of Functionalized Naphthalenes/Solvatochromic Dyes

Microwave-assisted Functionalization of Poly(ethylene glycol) and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation

One of the main benefits to using poly(ethylene glycol) (PEG) macromers in hydrogel formation is synthetic versatility. The ability to draw from a large variety of PEG molecular weights and configurations (arm number, arm length, and branching pattern) affords researchers tight control over resulting hydrogel structures and properties, including Young&#8217;s modulus and mesh size. This video will illustrate a rapid, efficient, solvent-free, microwave-assisted method to methacrylate PEG precursors into poly(ethylene glycol) dimethacrylate (PEGDM). This synthetic method provides much-needed starting materials for applications in drug delivery and regenerative medicine. The demonstrated method is superior to traditional methacrylation methods as it is significantly faster and simpler, as well as more economical and environmentally friendly, using smaller amounts of reagents and solvents. We will also demonstrate an adaptation of this technique for on-resin methacrylamide functionalization of peptides. This on-resin method allows the N-terminus of peptides to be functionalized with methacrylamide groups prior to deprotection and cleavage from resin. This allows for selective addition of methacrylamide groups to the N-termini of the peptides while amino acids with reactive side groups (e.g.&#160;primary amine of lysine, primary alcohol of serine, secondary alcohols of threonine, and phenol of tyrosine) remain protected, preventing functionalization at multiple sites. This article will detail common analytical methods (proton Nuclear Magnetic Resonance spectroscopy (;H-NMR) and Matrix Assisted Laser Desorption Ionization Time of Flight mass spectrometry (MALDI-ToF)) to assess the efficiency of the functionalizations. Common pitfalls and suggested troubleshooting methods will be addressed, as will modifications of the technique which can be used to further tune macromer functionality and resulting hydrogel physical and chemical properties. Use of synthesized products for the formation of hydrogels for drug delivery and cell-material interaction studies will be demonstrated, with particular attention paid to modifying hydrogel composition to affect mesh size, controlling hydrogel stiffness and drug release.

Microwave-assisted Functionalization of Polyethylene glycol and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation

This video will illustrate a rapid, efficient method to methacrylate poly(ethylene glycol), enabling chain polymerizations and hydrogel synthesis. It will demonstrate how to similarly introduce methacrylamide functionalities into peptides, detail common analytical methods to assess functionalization efficiency, provide suggestions for troubleshooting and advanced modifications, and demonstrate typical hydrogel characterization techniques.

전자 레인지를 이용한 폴리의 기능화 (에틸렌 글리콜) 및 체인 중합 및 하이드로 겔 형성에있는 사용을위한 온 수지 펩티드

One of the main benefits to using poly(ethylene glycol) (PEG) macromers in hydrogel formation is synthetic versatility. The ability to draw from a large ...

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화학

Preparation of Silica Nanoparticles Through Microwave-assisted Acid-catalysis

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle diameters ranging from 30-250 nm by varying the reaction conditions. Through the selection of a microwave compatible solvent, silicic acid precursor, catalyst, and microwave irradiation time, these microwave-assisted methods were capable of overcoming the previously reported shortcomings associated with synthesis of silica nanoparticles using microwave reactors. The siloxane precursor was hydrolyzed using the acid catalyst, HCl. Acetone, a low-tan &#948; solvent, mediates the condensation reactions and has minimal interaction with the electromagnetic field. Condensation reactions begin when the silicic acid precursor couples with the microwave radiation, leading to silica nanoparticle sol formation. The silica nanoparticles were characterized by dynamic light scattering data and scanning electron microscopy, which show the materials&#39; morphology and size to be dependent on the reaction conditions. Microwave-assisted reactions produce silica nanoparticles with roughened textured surfaces that are atypical for silica sols produced by St&#246;ber&#39;s methods, which have smooth surfaces.

Silica nanoparticles were prepared using acid-catalysis of a siloxane precursor and microwave-assisted synthetic techniques resulting in the controlled growth of nanomaterials ranging from 30-250 nm in diameter. The growth dynamics can be controlled by varying the initial silicic acid concentration, time of the reaction, and temperature of reaction.

전자 레인지를 이용한 산 - 촉매 반응을 통해 실리카 나노 입자의 제조

Microwave-assisted synthetic techniques were used to quickly and reproducibly produce silica nanoparticle sols using an acid catalyst with nanoparticle ...

Synthesis and Characterization of Functionalized Metal-organic Frameworks

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and technological applications. Their signature property is their ultrahigh porosity, which however imparts a series of challenges when it comes to both constructing them and working with them. Securing desired MOF chemical and physical functionality by linker/node assembly into a highly porous framework of choice can pose difficulties, as less porous and more thermodynamically stable congeners (e.g., other crystalline polymorphs, catenated analogues) are often preferentially obtained by conventional synthesis methods. Once the desired product is obtained, its characterization often requires specialized techniques that address complications potentially arising from, for example, guest-molecule loss or preferential orientation of microcrystallites. Finally, accessing the large voids inside the MOFs for use in applications that involve gases can be problematic, as frameworks may be subject to collapse during removal of solvent molecules (remnants of solvothermal synthesis). In this paper, we describe synthesis and characterization methods routinely utilized in our lab either to solve or circumvent these issues. The methods include solvent-assisted linker exchange, powder X-ray diffraction in capillaries, and materials activation (cavity evacuation) by supercritical CO2 drying. Finally, we provide a protocol for determining a suitable pressure region for applying the Brunauer-Emmett-Teller analysis to nitrogen isotherms, so as to estimate surface area of MOFs with good accuracy.

Synthesis, activation, and characterization of intentionally designed metal-organic framework materials is challenging, especially when building blocks are incompatible or unwanted polymorphs are thermodynamically favored over desired forms. We describe how applications of solvent-assisted linker exchange, powder X-ray diffraction in capillaries and activation via supercritical CO2 drying, can address some of these challenges.

기능화의 합성 및 특성 금속 - 유기 프레임 워크

Metal-organic frameworks have attracted extraordinary amounts of research attention, as they are attractive candidates for numerous industrial and ...

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ethylene-propylene rubber, grafted with maleic anhydride, is thermo-reversibly cross-linked in two steps. The pending anhydride moieties are first modified with furfurylamine to graft furan groups to the rubber backbone. These pendant furan groups are then cross-linked with a bis-maleimide via a Diels-Alder coupling reaction. Both reactions can be performed under a broad range of experimental conditions and can easily be applied on a large scale. The material properties of the resulting Diels-Alder cross-linked rubbers are similar to a peroxide-cured ethylene/propylene/diene rubber (EPDM) reference. The cross-links break at elevated temperatures (&#62; 150 &#176;C) via the retro-Diels-Alder reaction and can be reformed by thermal annealing at lower temperatures (50-70 &#176;C). Reversibility of the system was proven with infrared spectroscopy, solubility tests and mechanical properties. Recyclability of the material was also shown in a practical way, i.e., by cutting a cross-linked sample into small parts and compression molding them into new samples displaying comparable mechanical properties, which is not possible for conventionally cross-linked rubbers.

A simple two-step approach involving rubber modification and cross-linking yields fully reworkable, elastic rubber products.

열 가역적 가교 고무 통해 딜스 - 알더 화학의 준비 및 등록

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ...

Synthesis of Plant Phenol-derived Polymeric Dyes for Direct or Mordant-based Hair Dyeing

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been previously demonstrated. However, the dyeing process takes a long time to complete compared to commercial hair-dyeing products. To overcome this bottleneck, pre-synthesized polymeric products of the oxidative reaction of Trametes versicolor laccase on catechin and catechol, either with or without mordant agents (e.g., FeSO4), were here employed to achieve permanent keratin hair dyeing in various colors and shades. The laccase action in acidic sodium acetate buffer led to a deep black coloration after coupling reactions between the plant phenols. The colored dye products were then desalted and concentrated with ultrafiltration. The dyes, with or without mordant agents, caused a significant increase in &#916;E values (i.e., color difference value) in gray human hair within 2.5 hours. In addition, different keratin colors and shades were induced depending upon the mordanting and pH changes. The dyed hair also exhibited a strong resistance to detergent treatments, indicating that our methods can give rise to permanent hair dyeing.&#160;Overall, our work has provided novel insight into developing eco-friendly hair-dyeing methods as alternatives to commercial toxic diamine-based dyes.

Here, we present a protocol to use pre-synthesized polymeric products derived from fungal laccase-catalyzed polymerization of plant phenols, either with or without mordant agents (e.g., FeSO4), to induce detergent-resistant keratin hair dyeing within 2.5 hours.

직접 또는 모던 기반 머리 염색에 대한 공장 페놀 유래 고분자 염료의 합성

Effective hair dyeing through in situ incubation of keratin hair with the products of fungal laccase-catalyzed polymerization of plant phenols has been ...

One-pot Microwave-assisted Conversion of Anomeric Nitrate-esters to Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate glycosyl donor. Following azido-nitration of a glycal, the product 2-azido-1-nitrate ester can be hydrolyzed under microwave-assisted irradiation. This transformation is usually achieved using strongly nucleophilic reagents and extended reaction times. Microwave irradiation induces hydrolysis, in the absence of reagents, with short reaction times. Following denitration, the intermediate anomeric alcohol is converted, in the same pot, to the corresponding 2-azido-1-trichloroacetimidate.

A 2-azido-1-nitrate-ester can be converted to the corresponding 2-azido-1-trichloroacetimidate in a one-pot procedure. The goal of the manuscript is to demonstrate utility of the microwave reactor in carbohydrate synthesis.

한 냄비 전자 렌지를 이용한 변환 Anomeric 질 산 에스테 르의 Trichloroacetimidates

The goal of the following procedure is to provide a demonstration of the one-pot conversion of a 2-azido-1-nitrate-ester to a trichloroacetimidate ...

Enzymatic Cascade Reactions for the Synthesis of Chiral Amino Alcohols from L-lysine

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. Their synthesis by conventional organic chemistry often requires tedious multi-step synthesis processes, with difficult control of the stereochemical outcome. We present a protocol to enzymatically synthetize amino alcohols starting from the readily available L-lysine in 48 h. This protocol combines two chemical reactions that are very difficult to conduct by conventional organic synthesis. In the first step, the regio- and diastereoselective oxidation of an unactivated C-H bond of the lysine side-chain is catalyzed by a dioxygenase; a second regio- and diastereoselective oxidation catalyzed by a regiodivergent dioxygenase can lead to the formation of the 1,2-diols. In the last step, the carboxylic group of the alpha amino acid is cleaved by a pyridoxal-phosphate (PLP) decarboxylase (DC). This decarboxylative step only affects the alpha carbon of the amino acid, retaining the hydroxy-substituted stereogenic center in a beta/gamma position. The resulting amino alcohols are therefore optically enriched. The protocol was successfully applied to the semipreparative-scale synthesis of four amino alcohols. Monitoring of the reactions was conducted by high performance liquid chromatography (HPLC) after derivatization by 1-fluoro-2,4-dinitrobenzene. Straightforward purification by solid-phase extraction (SPE) afforded the amino alcohols with excellent yields (93% to &#62;95%).

Chiral amino alcohols are versatile molecules for use as scaffolds in organic synthesis. Starting from L-lysine, we synthesize amino alcohols by an enzymatic cascade reaction combining diastereoselective C-H oxidation catalyzed by dioxygenase followed by cleavage of the carboxylic acid moiety of the corresponding hydroxyl amino acid by a decarboxylase.

패-리 신에서 랄 아미노 알콜의 합성을 위한 효소 캐스케이드 반응

Amino alcohols are versatile compounds with a wide range of applications. For instance, they have been used as chiral scaffolds in organic synthesis. ...

Reducing Willow Wood Fuel Emission by Low Temperature Microwave Assisted Hydrothermal Carbonization

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative environmental impact and slag formation. The selected short rotation coppice (SRC) willow wood has a high ash content (<img alt="Equation 1" src="/files/ftp_upload/58970/58970eq1.jpg" /> = 1.96%) and, therefore, a high content of emission and slag precursors. Therefore, the reduction of minerals from SRC willow wood by low temperature microwave assisted hydrothermal carbonization (MAHC) at 150 &#176;C, 170 &#176;C, and 185 &#176;C is investigated. An advantage of MAHC over conventional reactors is an even temperature conductance in the reaction medium, as microwaves penetrate the whole reactor volume. This allows a better temperature control and a faster cooldown. Therefore, a succession of depolymerization, transformation and repolymerization reactions can be analyzed effectively. In this study, the analysis of the mass loss, ash content and composition, heating values and molar O/C and H/C ratios of the treated and untreated SCR willow wood showed that the mineral content of the MAHC coal was reduced and the heating value increased. The process water showed a decreasing pH and contained furfural and 5-methylfurfural. A process temperature of 170 &#176;C showed the best combination of energy input and ash component reduction. The MAHC allows a better understanding of the hydrothermal carbonization process, while a large-scale industrial application is unlikely because of the high investment costs.

A protocol for the emission precursor depletion from low quality biomass by low temperature microwave assisted hydrothermal carbonization treatment is presented. This protocol includes the microwave parameters and the analysis of the biocoal product and process water.

저온 마이크로파 보조 열 량 화에의 한 버드 나무 연료 방출 감소

Biomass is a sustainable fuel, as its CO2 emissions are reintegrated in biomass growth. However, the inorganic precursors in the biomass cause a negative ...

Pretargeted Radioimmunotherapy Based on the Inverse Electron Demand Diels-Alder Reaction

While radioimmunotherapy (RIT) is a promising approach for the treatment of cancer, the long pharmacokinetic half-life of radiolabeled antibodies can result in high radiation doses to healthy tissues. Perhaps not surprisingly, several different strategies have been developed to circumvent this troubling limitation. One of the most promising of these approaches is pretargeted radioimmunotherapy (PRIT). PRIT is predicated on decoupling the radionuclide from the immunoglobulin, injecting them separately, and then allowing them to combine in vivo at the target tissue. This approach harnesses the exceptional tumor-targeting properties of antibodies while skirting their pharmacokinetic drawbacks, thereby lowering radiation doses to non-target tissues and facilitating the use of radionuclides with half-lives that are considered too short for use in traditional radioimmunoconjugates. Over the last five years, our laboratory and others have developed an approach to in vivo pretargeting based on the inverse electron-demand Diels-Alder (IEDDA) reaction between trans-cyclooctene (TCO) and tetrazine (Tz). This strategy has been successfully applied to pretargeted positron emission tomography (PET) and single-photon emission computed tomography (SPECT) imaging with a variety of antibody-antigen systems. In a pair of recent publications, we have demonstrated the efficacy of IEDDA-based PRIT in murine models of pancreatic ductal adenocarcinoma and colorectal carcinoma. In this protocol, we describe protocols for PRIT using a 177Lu-DOTA-labeled tetrazine radioligand ([177Lu]Lu-DOTA-PEG7-Tz) and a TCO-modified variant of the colorectal cancer targeting huA33 antibody (huA33-TCO). More specifically, we will describe the construction of huA33-TCO, the synthesis and radiolabeling of [177Lu]Lu-DOTA-PEG7-Tz, and the performance of in vivo biodistribution and longitudinal therapy studies in murine models of colorectal carcinoma.

This protocol describes the synthesis and characterization of a trans-cyclooctene (TCO)-modified antibody and a 177Lu-labeled tetrazine (Tz) radioligand for pretargeted radioimmunotherapy (PRIT). In addition, it details the use of these two constructs for in vivo biodistribution and longitudinal therapy studies in a murine model of colorectal cancer.

Pretargeted Radioimmunotherapy 역 전자 수요 Diels 오리 나무 반응에 따라

While radioimmunotherapy (RIT) is a promising approach for the treatment of cancer, the long pharmacokinetic half-life of radiolabeled antibodies can ...

Efficient Synthesis of All-Carbon Quaternary Centers via the Conjugate Addition of Functionalized Monoorganozinc Bromides

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the preparation of all-carbon quaternary centers. Though conjugate additions of organometallic reagents are typically performed utilizing highly reactive organolithium or Grignard reagents, organozinc reagents have garnered attention for their enhanced chemoselectivity and mild reactivity. Despite numerous recent advances with more reactive diorganozinc and mixed diorganozinc reagents, the generation of all-carbon quaternary centers via the conjugate addition of functionalized monoorganozinc reagents remains a challenge. This protocol details a convenient and mild &#8220;one-pot&#8221; preparation and copper mediated conjugate addition of functionalized monoorganozinc bromides to cyclic &#945;,&#946;-unsaturated carbonyls to afford a broad scope of all-carbon quaternary centers in generally excellent yield and diastereoselectivity. Key to the development of this technology is the utilization of DMA as a reaction solvent with TMSCl as a Lewis acid. Notable advantages to this methodology include the operational simplicity of the organozinc reagent preparation afforded by the utilization of DMA as a solvent, as well as an efficient conjugate addition mediated by various Cu(I) and Cu(II) salts. Moreover, an intermediate silyl enol ether can be isolated utilizing a modified workup procedure. The substrate scope is limited to cyclic unsaturated ketones, and the conjugate addition is impeded by stabilized (e.g., allyl, enolate, homoenolate) and sterically encumbered (e.g., neopentyl, o-aryl) monoorganozinc reagents. Conjugate additions to five- and seven-membered rings were effective, albeit in lower yields compared with six-membered ring substrates.

A simple and practical protocol for the efficient conjugate addition of functionalized monoorganozinc bromides to cyclic &#945;,&#946;-unsaturated carbonyls to furnish all-carbon quaternary centers was developed.

관 능 적 모노 아연 브로 미 데스의 결합체 첨가를 통한 전 탄소 4 급 센터의 효율적인 합성

The conjugate addition of organometallic reagents to &#945;,&#946;-unsaturated carbonyls represents an important method to generate C&#8211;C bonds in the ...