Click chemistry mediated synthesis of bio-inspired phosphonyl-functionalized ionic liquids

Braun, Richard A.; Bradfield, Joseph L.; Henderson, Codey B.; Mobarrez, Niloufar; Sheng, Yinghong; O’Brien, Richard A.; Stenson, Alexandra C.; Davis, Jr. James H.; Mirjafari, Arsalan

doi:10.1039/c4gc01933d

Cited by 12 publications

(5 citation statements)

References 110 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In various environmental, biological, medical, and pharmaceutical applications corresponding to the list of uses given above but also used in many other cases, − ILs that contain naturally-derived materials seem to be extremely desirable, mainly because of the introduction of green − and economic aspects , and sometimes also because of high availability . Strong bioactive capabilities of natural origin substances are the key platform of biological capabilities that should be used to implement and/or strengthen bioapplications when adopted to ionic salt structures …”

Section: Introductionmentioning

confidence: 99%

Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products

Feder‐Kubis

Czerwoniec

Lewandowski

et al. 2019

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

One of the major problems in environmental industries is plant protection using ecologically and human friendly plant resistance inducers. To address this problem in an advantageous way, we used plant sources and substance that is responsible for plant resistance induction as the starting materials to synthesize new ionic liquids (ILs). Engineered ammonium and imidazolium salts with excellent yields of ≥98% were obtained under mild process conditions, using the (−)-menthol moiety, which is economically viable, widely used in many industries, and easily available from natural origins. This monoterpene alcohol, derived from renewable raw resources, was introduced to the cation part of the synthesized ILs. As a counterion, benzo[1.2.3]thiadiazole-7-carboxylate, which has resistance induction properties in plants, was introduced. In this study, we demonstrated that the careful design of IL’s cations and anions leads to new dual function compounds. This biological property manifests itself as a high level of antimicrobiological activity of the obtained salts, which allows new compounds to be concurrently classified as antimicrobial agents and at the same time as plant resistance inducers. Tested ammonium and imidazolium ILs exhibited antimicrobial activities higher than benzalkonium chloride, which is commonly used in biocides. When analyzing ILs, it was noted that the length of the alkyl chain, presence of the naturally occurring substituent, type of anion, type of cation core, and steric hindrance of the cyclic group are the principal factors determining antimicrobial properties. Work presented in this article shows one of the possibilities of enhancing biological properties, such as resistance induction, of the ILs, by pairing them in a sustainable manner with the antibiocidal agent to form bifunctional salts. Using this approach, it is possible to prepare bifunctional salts that maintain their systemic acquired resistance induction activity at very high levels, enhance solubility in water owing to their ionic characteristics, and deliver additional activities, such as antibacterial. Our design strategy indicates that the choice of the IL components can result in antimicrobial SAR plant resistance inducers, which might be successfully applied as disinfectants or plant resistance inducers.

show abstract

Section: Introductionmentioning

confidence: 99%

Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products

Feder‐Kubis

Czerwoniec

Lewandowski

et al. 2019

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

show abstract

“…9,10 Bioionic liquids are a group of ILs entirely comprising renewable natural resources. 11 Their unabated popularity is related to the fact that these compounds are usually less harmful to the environment and are more readily biodegradable than the ILs obtained from synthetic substrates. 12,13 Naturally occurring L-carnitine, choline, or betaine cations are used to synthesize the majority of the bio-ILs, 14,15 while derivatives of fatty acids and carboxylic acids, such as acetic or formic acid, are often utilized as the source of the anion.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Bioionic liquids are a group of ILs entirely comprising renewable natural resources . Their unabated popularity is related to the fact that these compounds are usually less harmful to the environment and are more readily biodegradable than the ILs obtained from synthetic substrates. , Naturally occurring l -carnitine, choline, or betaine cations are used to synthesize the majority of the bio-ILs, , while derivatives of fatty acids and carboxylic acids, such as acetic or formic acid, are often utilized as the source of the anion. ,, Bio-ILs derived from amino acids or sugars have also recently been described in the literature. − Another bioinspired approach, based on merging an ion of natural origin with the synthetic counterion, proved to possess many advantages, such as facilitating the implementation of the desired properties while reducing adverse impacts on the environment.…”

Section: Introductionmentioning

confidence: 99%

Ionic Liquids Derived from Vitamin C as Multifunctional Active Ingredients for Sustainable Stored-Product Management

Niemczak

Kaczmarek

Klejdysz

et al. 2018

ACS Sustainable Chem. Eng.

View full text Add to dashboard Cite

This study is focused on the utilization of naturally occurring ascorbic acid (vitamin C) in the synthesis of biologically inspired ionic liquids with attractive application potential. The ionic liquids with the ascorbate anion were obtained in high yield (>90%) via a simple, "green" two-step procedure using well-known, cost-effective, and commercially available alkyltrimethylammonium, dialkyldimethylammonium, and alkylmethylbis(2hydroxyethyl)ammonium cations. Three positive ions in this group used for syntheses are derived from renewable resources, such as vegetable oil or animal fat. The study confirmed the strong influence of the chemical structure of the cation on the stability of the compounds obtained in the air, as well as in aqueous solutions. In addition, the synthesized ionic forms of vitamin C exhibited very good antibacterial and antifungal properties against different microorganisms, including pathogens. The tests also revealed the excellent or good deterrent activity toward common stored-grain insects (granary weevil, confused flour beetle, and khapra beetle), reaching the values determined for azadirachtin, known as the reference antifeedant. The best results were achieved with products containing two long alkyl substituents in the cation (dimethyldioctylammonium and didecyldimethylammonium) that proved to be extremely effective against all the organisms tested. The results of the biological activity indicate that the products synthesized belong to the third generation of ionic liquids. In conclusion, ascorbate-based ionic liquids with multifunctional (antibacterial, antifungal, antifeedant, and antioxidant) properties have substantial potential to be used in the storage of crop protection products.

show abstract

“…In recent decades, transition‐metal‐catalyzed C–P coupling has emerged as one of the most important and straightforward tools for synthesizing alkenylphosphorus compounds among the existing approaches . The addition of P(O)H compounds to alkynes catalyzed by Pd, Rh, Zr, Ni, Cu, Mo or Mn is an efficient method for C(sp 2 )−P bond formation. Additionally, the reaction of vinylphosphonates or H‐phosphonates with different coupling partners bearing a halogen, a trifluoromethanesulfonate group, or a B(OH) 2 group can be also used to synthesize vinylphosphonates.…”

Section: Introductionmentioning

confidence: 99%

Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp²)−P Bond Formation

et al. 2017

View full text Add to dashboard Cite

The first solvent-controlled copper-catalyzed oxidative decarboxylative coupling of alkenyl acids with P(O)H compoundsf or alkenyl C(sp 2 )ÀPb ond formation by af reeradical process is reported. Ther eactione nables the highly chemo-and stereoselective synthesis of various( E)-alkenylphosphonates and (E)-alkenylphosphinate oxidesi nm oderate to good yields. On the basis of this catalytic system, styr-enes and b-nitrostyrene as well as alkenyl acids can also give the corresponding products by cross-dehydrogenative coupling andd enitration, respectively.B ya lteringt he oxidant, the oxyphosphorylation of styrenes with P(O)H compounds readily yields b-ketophosphonates. The reactiond escribed here enables av ersatile and practical avenue for the formation of valuable CÀPb onds.[a] Dr.Scheme2.Reactionconditions: 1 (0.40 mmol), 2a (0.25 mmol), Cu(OAc) 2 ·H 2 O (7.5 mol %), K 2 S 2 O 8 (0.75 mmol),C H 3 CN (1.0 mL), 24 h, N 2 ;i solatedy ield. Scheme3.Reactionconditions: 1 (0.40 mmol), 2 (0.25 mmol), Cu(OAc) 2 ·H 2 O (7.5 mol %), K 2 S 2 O 8 (0.75 mmol), CH 3 CN (1.0 mL),2 4h,N 2 ;isolated yield. Scheme4.Control experiments. 9 (d, J C-P = 5.3 Hz), 15.4 ppm (d, J C-P = 6.5 Hz); 31 PNMR (162 MHz, CDCl 3 ): d = 19.3 ppm; 19 FNMR (376 MHz, CDCl 3 ): d = À109.8 ppm;H RMS (ESI-TOF): m/z:c alcd for C 12 H 17 FO 3 P: 259.0899 [M+ +H] + ;f ound:2 59.0912;c alcd for C 24 H 33 F 2 O 6 P 2 : 517.1720 [2 M+ +H] + ;found:5 17.1738. Diethyl (E)-(3-fluorostyryl)phosphonate (3 ja). 1 HNMR (400 MHz, CDCl 3 ): d = 7.50-7.24 (m, 4H), 7.20-7.17 (d, 1 HNMR (400 MHz, CDCl 3 ): d = 7.80-7.73 (m, 5H), 7.70-7.68 (d, J = 7.8 Hz, 1H), 7.63-7.47 (m, 9H), 6.98-6.88 ppm (dd, J = 21.8, 17.4 Hz, 1H); 13 CNMR (100 MHz, CDCl 3 ): d = 145.9 (d, J C-P = 3.6 Hz), 135.9 (d, ppm (d, J C-P = 101.9 Hz); 31 PNMR (162 MHz, CDCl 3 ): d = 24.0 ppm; 19 FNMR (376 MHz, CDCl 3 ): d = À62.8 ppm;H RMS (ESI-TOF): m/z: Asian

show abstract

Click chemistry mediated synthesis of bio-inspired phosphonyl-functionalized ionic liquids

Cited by 12 publications

References 110 publications

Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products

Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products

Ionic Liquids Derived from Vitamin C as Multifunctional Active Ingredients for Sustainable Stored-Product Management

Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp²)−P Bond Formation

Contact Info

Product

Resources

About

Click chemistry mediated synthesis of bio-inspired phosphonyl-functionalized ionic liquids

Cited by 12 publications

References 110 publications

Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products

Ionic Liquids with Natural Origin Component: A Path to New Plant Protection Products

Ionic Liquids Derived from Vitamin C as Multifunctional Active Ingredients for Sustainable Stored-Product Management

Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp2)−P Bond Formation

Contact Info

Product

Resources

About

Solvent‐Controlled Copper‐Catalyzed Radical Decarboxylative Coupling for Alkenyl C(sp²)−P Bond Formation