PEG400-enhanced synthesis of gem-dichloroaziridines and gem-dichlorocyclopropanes via in situ generated dichlorocarbene

Song, Qing‐Wen; Yu, Bing; Liu, Anhua; He, Youzhou; Yang, Zhenzhen; Diao, Zhen‐Feng; Song, Qingchuan; Li, Xuedong; He, Liang‐Nian

doi:10.1039/c3ra43307b

Cited by 18 publications

(11 citation statements)

References 46 publications

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“…Our synthetic strategy is shown in Scheme 1. MeO-gDCC containing 1 was prepared from the selective cyclopropanation of the electron-rich alkene of commercially available 1methoxyl-1,4-cyclohexadiene using a protocol 32 that avoids the tedious workup involved with conventional phase transfer agents (e.g., tetrabutylammonium salts). Subsequent ozonolysis and reduction produces diol 2 as a colorless oil.…”

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confidence: 99%

A Latent Mechanoacid for Time-Stamped Mechanochromism and Chemical Signaling in Polymeric Materials

2019

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Mechanically coupled proton transduction offers potential for stress-responsive polymeric materials whose properties can be switched via acid-triggered coloration, polymerization/cross-linking, or degradation. The utility of currently available mechanoacids, however, is limited by modest force-free stability or a scissile response that caps mechanoacid generation at one proton per strained polymer chain. Here, we report a new mechanoacid based on 2-methoxy-substituted gem-dichlorocyclopropane (MeO-gDCC). Pulsed ultrasonication leads to the mechanochemical ring opening of the MeO-gDCC and the subsequent elimination of either HCl or MeCl, with ∼0.58 equiv of HCl released per mechanophore activation and ∼67 protons per chain scission event. Single-molecule force spectroscopy reveals that the methoxy substituent lowers the force required for rapid (k open ∼102 s–1) ring opening to ca. 900 pN, vs 1300 pN required for the parent gDCC. The utility of the mechanoacid is demonstrated in silicone elastomers, where its mechanical activation leads to a strain-triggered color change prior to fracture of the elastomer. The postactivation kinetics of coloration are used to demonstrate a new concept in mechanochromism, namely, a spectroscopic indicator of not only whether and where a mechanical event has occurred but when it occurred.

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confidence: 99%

A Latent Mechanoacid for Time-Stamped Mechanochromism and Chemical Signaling in Polymeric Materials

2019

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“…Subsequently, [HMTH] 2 H 2 [SiW 12 O 40 ] (3 mol %) was applied as catalyst for the optimization of different green solvents − including polyethylene glycols, i.e., PEG200 and PEG400, cyclopentyl methyl ether (CPME), dimethyl carbonate (DMC), ethylene carbonate (EC), propylene carbonate (PC). As can be seen in Figure A, only 1% and 2% yields were observed when the reaction was conducted in PEG200 and PEG400, respectively.…”

Section: Resultsmentioning

confidence: 99%

Ionic Liquid from Vitamin B1 Analogue and Heteropolyacid: A Recyclable Heterogeneous Catalyst for Dehydrative Coupling in Organic Carbonate

Yang

Xun

et al. 2019

ACS Sustainable Chem. Eng.

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The ionic liquid [HMTH]2H2[SiW12O40] was prepared from the inexpensive, nontoxic vitamin B1-like compound, i.e., 5-(2-hydroxyethyl)-4-methylthiazole (HMT), and the noncorrosive heteropolyacid (H4SiW12O40). This acidic ionic liquid was found to be an efficient heterogeneous catalyst for the direct dehydrative coupling of alcohols with alcohols (or alkenes) to synthesize various polysubstituted olefins in good to excellent yields with dimethyl carbonate (DMC) as a green solvent. Furthermore, this protocol was applicable in a gram-scale reaction, and the catalyst could be used at least for 8 runs without significant loss of activity.

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“…Commercially available 2-iodopropane ( 2a ), cyclohexyl iodide ( 2b ), and 1,1,1-trifluoro-3-iodopropane ( 2c ) were distilled prior to use. Reagents shown below were synthesized according to literature procedures: N -methyl-1-phenylmethanimine ( 1a ), N -(2-methoxyethyl)-1-phenylmethanimine ( 1b ), 1-(3-methoxyphenyl)- N -methylmethanimine ( 1c ), methyl 2-(benzylideneamino)acetate ( 1d ), 2-(benzylideneamino)- N , N -dimethylethan-1-amine ( 1e ), N ,1-diphenylmethanimine ( 1f ), N -allyl-1-phenylmethanimine ( 1g ), N -benzyl-1-phenylmethanimine ( 1h ), N -cyclopropyl-1-phenylmethanimine ( 1i ), 1-(4-chlorophenyl)- N -phenylmethanimine ( 4a ), 1-(4-methoxyphenyl)- N -phenylmethanimine ( 4b ), N -(4-bromophenyl)-1-phenylmethanimine ( 4c ), 1-(4-methoxyphenyl)- N -(p-tolyl)methanimine ( 4d ), N ,1-bis(4-methoxyphenyl)methanimine ( 4e ), 1-(furan-2-yl)- N -(4-methoxyphenyl)methanimine ( 4f ), N -benzylidene-4-methylbenzenesulfonamide ( 6 ), tert -butyl 4-iodopiperidine-1-carboxylate ( 2d ), (3-iodobutyl)benzene ( 2e ), (3-iodopropyl)benzene ( 2f ), 4-iodobut-1-ene ( 2g ), ethyl 4-iodobutanoate ( 2h ), 4-iodobutanenitrile ( 2i ), (iodomethyl)trimethylsilane ( 2j ), 4-iodobutyl pivalate ( 2k ), iodocyclooctane ( 2f ), 1-iodo-2-methylpropane ( 2m ), 5-iodopent-1-ene ( 2n ), 1,3-dioxoisoindolin-2-yl cyclohexanecarboxylate ( 8 ), 2,4,6-tris(diphenylamino)-3,5-difluorobenzonitrile (3DPA2FBN) …”

Section: Methodsmentioning

confidence: 99%

Photoredox Promoted Barbier-Type Reaction of Alkyl Iodides with N-Alkyl and N-Aryl Imines

2023

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PEG400-enhanced synthesis of gem-dichloroaziridines and gem-dichlorocyclopropanes via in situ generated dichlorocarbene

Cited by 18 publications

References 46 publications

A Latent Mechanoacid for Time-Stamped Mechanochromism and Chemical Signaling in Polymeric Materials

A Latent Mechanoacid for Time-Stamped Mechanochromism and Chemical Signaling in Polymeric Materials

Ionic Liquid from Vitamin B1 Analogue and Heteropolyacid: A Recyclable Heterogeneous Catalyst for Dehydrative Coupling in Organic Carbonate

Photoredox Promoted Barbier-Type Reaction of Alkyl Iodides with N-Alkyl and N-Aryl Imines

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