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Search for "flame retardant" in Full Text gives 5 result(s) in Beilstein Journal of Organic Chemistry.
Phosphonic acid: preparation and applications
- Charlotte M. Sevrain,
- Mathieu Berchel,
- Hélène Couthon and
- Paul-Alain Jaffrès
Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219
- were also considered for their flame retardant properties [116]. All these applications, that cover a very broad panel of scientific topics, point out the great interest of phosphonic acids.The next sections report the most important and efficient methods to produce phosphonic acids. 3. Preparation of
- . First, a mechanochemical cracking yielded carboradical intermediates that were reacted with red phosphorus and then oxidized in the presence of air to produce graphene phosphonic acid 137 [116] (Figure 39). This material which is water soluble was used as a non-toxic flame-retardant. Conclusion
Graphical Abstract
Figure 1: Summary of the synthetic routes to prepare phosphonic acids detailed in this review. The numbers in...
Figure 2: Chemical structure of dialkyl phosphonate, phosphonic acid and illustration of the simplest phospho...
Figure 3: Illustration of some phosphonic acid exhibiting bioactive properties. A) Phosphonic acids for biome...
Figure 4: Illustration of the use of phosphonic acids for their coordination properties and their ability to ...
Figure 5: Hydrolysis of dialkyl phosphonate to phosphonic acid under acidic conditions.
Figure 6: Examples of phosphonic acids prepared by hydrolysis of dialkylphosphonate with HCl 35% at reflux (16...
Figure 7: A) and B) Observation of P–C bond breaking during the hydrolysis of phosphonate with concentrated H...
Figure 8: Mechanism of the hydrolysis of dialkyl phosphonate with HCl in water.
Figure 9: Hydrolysis of bis-tert-butyl phosphonate 28 into phosphonic acid 29 [137].
Figure 10: A) Hydrolysis of diphenyl phosphonate into phosphonic acid in acidic media. B) Examples of phosphon...
Figure 11: Suggested mechanism occurring for the first step of the hydrolysis of diphenyl phosphonate into pho...
Figure 12: A) Hydrogenolysis of dibenzyl phosphonate to phosphonic acid. B) Compounds 33, 34 and 35 were prepa...
Figure 13: A) Preparation of phosphonic acid from diphenyl phosphonate with the Adam’s catalyst. B) Compounds ...
Figure 14: Suggested mechanism for the preparation of phosphonic acid from dialkyl phosphonate using bromotrim...
Figure 15: A) Reaction of the phosphonate-thiophosphonate 37 with iodotrimethylsilane followed by methanolysis...
Figure 16: Synthesis of hydroxymethylenebisphosphonic acid by reaction of tris(trimethylsilyl) phosphite with ...
Figure 17: Synthesis of the phosphonic acid disodium salt 48 by reaction of mono-hydrolysed phosphonate 47 wit...
Figure 18: Phosphonic acid synthesized by the sequence 1) bromotrimethylsilane 2) methanolysis or hydrolysis. ...
Figure 19: Polyphosphonic acids and macromolecular compounds prepared by the hydrolysis of dialkyl phosphonate...
Figure 20: Examples of organometallic complexes functionalized with phosphonic acids that were prepared by the...
Figure 21: Side reaction observed during the hydrolysis of methacrylate monomer functionalized with phosphonic...
Figure 22: Influence of the reaction time during the hydrolysis of compound 76.
Figure 23: Dealkylation of dialkyl phosphonates with boron tribromide.
Figure 24: Dealkylation of diethylphosphonate 81 with TMS-OTf.
Figure 25: Synthesis of substituted phenylphosphonic acid 85 from the phenyldichlorophosphine 83.
Figure 26: Hydrolysis of substituted phenyldichlorophosphine oxide 86 under basic conditions.
Figure 27: A) Illustration of the synthesis of chiral phosphonic acids from phosphonodiamides. B) Examples of ...
Figure 28: A) Illustration of the synthesis of the phosphonic acid 98 from phosphonodiamide 97. B) Use of cycl...
Figure 29: Synthesis of tris(phosphonophenyl)phosphine 109.
Figure 30: Moedritzer–Irani reaction starting from A) primary amine or B) secondary amine. C) Examples of phos...
Figure 31: Phosphonic acid-functionalized polymers prepared by Moedritzer–Irani reaction.
Figure 32: Reaction of phosphorous acid with imine in the absence of solvent.
Figure 33: A) Reaction of phosphorous acid with nitrile and examples of aminomethylene bis-phosphonic acids. B...
Figure 34: Reaction of carboxylic acid with phosphorous acid and examples of compounds prepared by this way.
Figure 35: Synthesis of phosphonic acid by oxidation of phosphinic acid (also identified as phosphonous acid).
Figure 36: Selection of reaction conditions to prepare phosphonic acids from phosphinic acids.
Figure 37: Synthesis of phosphonic acid from carboxylic acid and white phosphorus.
Figure 38: Synthesis of benzylphosphonic acid 136 from benzaldehyde and red phosphorus.
Figure 39: Synthesis of graphene phosphonic acid 137 from graphite and red phosphorus.
Dicarboxylic esters: Useful tools for the biocatalyzed synthesis of hybrid compounds and polymers
- Ivan Bassanini,
- Karl Hult and
- Sergio Riva
Beilstein J. Org. Chem. 2015, 11, 1583–1595, doi:10.3762/bjoc.11.174
- chemical means. The synthesized products can find a wide range of applications such as drug/gene delivery systems, flame retardant materials, conducting polymers, controlled release systems, diagnostic agents, and polymeric electrolytes for nano-crystalline solar cells. Curcumin (37) was converted to a
Graphical Abstract
Scheme 1: Activated derivatives of dicarboxylic acids.
Figure 1: Example of natural compounds selectively acylated with dicarboxylic esters.
Figure 2: C6-dicarboxylic acid diesters derivatives of NAG-thiazoline.
Figure 3: Sylibin dimers obtained by CAL-B catalyzed trans-acylation reactions.
Scheme 2: Biocatalyzed synthesis of paclitaxel derivatives.
Figure 4: 5-Fluorouridine derivatives obtained by CAL-B catalysis.
Scheme 3: Biocatalyzed synthesis of hybrid diesters 17 and 18.
Scheme 4: Hybrid derivatives of sylibin.
Figure 5: Bolaamphiphilic molecules containing (L)- and/or (D)-isoascorbic acid moieties.
Figure 6: Doxorubicin (29) trapped in a polyester made of glycolate, sebacate and 1,4-butandiol units.
Figure 7: Polyesters containing functionalized pentofuranose derivatives.
Figure 8: Polyesters containing disulfide moieties.
Figure 9: Polyesters containing epoxy moieties.
Figure 10: Biocatalyzed synthesis of polyesters containing glycerol.
Figure 11: Iataconic (34) and malic (35) acid.
Figure 12: Oxidized poly(hexanediol-2-mercaptosuccinate) polymer.
Figure 13: C-5-substituted isophthalates.
Figure 14: Curcumin-based polyesters.
Figure 15: Silylated polyesters.
Figure 16: Polyesters containing reactive ether moieties.
Figure 17: Polyesters obtained by CAL-B-catalyzed condensation of dicarboxylic esters and N-substituted dietha...
Figure 18: Polyesters comprising mexiletine (38) moieties.
Figure 19: Poly(amide-co-ester)s comprising a terminal hydroxy moiety.
Figure 20: Polymer comprising α-oxydiacid moieties.
Figure 21: Telechelics with methacrylate ends.
Figure 22: Telechelics with allyl-ether ends.
Figure 23: Telechelics with ends functionalized as epoxides.
Atherton–Todd reaction: mechanism, scope and applications
- Stéphanie S. Le Corre,
- Mathieu Berchel,
- Hélène Couthon-Gourvès,
- Jean-Pierre Haelters and
- Paul-Alain Jaffrès
Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117
- for biological applications. The selected examples to illustrate the applications of the Atherton–Todd reaction mainly cover the past 15 years. Keywords: amphiphiles; flame retardant; lipid conjugates; organophosphorus; phosphoramidate; phosphate; Review 1. Introduction The reaction of
- widely discussed in literature, is addressed. Then, the scope of this reaction is presented. Finally selected applications of this reaction are discussed. This selection mainly covers the applications of the past 15 years. A special focus is put on the synthesis of flame-retardant materials and the
Graphical Abstract
Scheme 1: Pioneer works of Atherton, Openshaw and Todd reporting on the synthesis of phosphoramidate starting...
Scheme 2: Mechanisms 1 (i) and 2 (ii) suggested by Atherton and Todd in 1945; adapted from [1].
Scheme 3: Two reaction pathways (i and ii) to produce chlorophosphate 2. Charge-transfer complex observed whe...
Scheme 4: Mechanism of the Atherton–Todd reaction with dimethylphosphite according to Roundhill et al. (adapt...
Scheme 5: Synthesis of dialkyl phosphate from dialkyl phosphite (i) and identification of chloro- and bromoph...
Scheme 6: Synthesis of chiral phosphoramidate with trichloromethylphosphonate as the suggested intermediate (...
Scheme 7: Selection of results that address the question of the stereochemistry of the AT reaction (adapted f...
Scheme 8: Synthesis of phenoxy spirophosphorane by the AT reaction (adapted from [34]).
Scheme 9: Suggested mechanism of the Atherton–Todd reaction, (i) and (ii) formation of chlorophosphate with a...
Scheme 10: AT reaction in biphasic conditions (adapted from [38]).
Scheme 11: AT reaction with iodoform as halide source (adapted from [37]).
Scheme 12: AT reaction with phenol at low temperature in the presence of DMAP (adapted from [40]).
Scheme 13: Synthesis of a triphosphate by the AT reaction starting with the preparation of chlorophosphate (ad...
Scheme 14: AT reaction with sulfonamide (adapted from [42]).
Scheme 15: Synthesis of a styrylphosphoramidate starting from the corresponding aniline (adapted from [43]).
Scheme 16: Use of hydrazine as nucleophile in AT reactions (adapted from [48]).
Scheme 17: AT reaction with phenol as a nucleophilic species; synthesis of dioleyl phosphate-substituted couma...
Scheme 18: Synthesis of β-alkynyl-enolphosphate from allenylketone with AT reaction (adapted from [58]).
Scheme 19: Synthesis of pseudohalide phosphate by using AT reaction (adapted from [67]).
Scheme 20: AT reaction with hydrospirophosphorane with insertion of CO2 in the product (adapted from [69]).
Scheme 21: AT reaction with diaryl phosphite (adapted from [70]).
Scheme 22: AT reaction with O-alkyl phosphonite (adapted from [71]).
Scheme 23: Use of phosphinous acid in AT reactions (adapted from [72]).
Scheme 24: AT reaction with secondary phosphinethiooxide (adapted from [76]).
Scheme 25: Use of H-phosphonothioate in the AT reaction (adapted from [78]).
Scheme 26: AT-like reaction with CuI as catalyst and without halide source (adapted from [80]).
Scheme 27: Reduction of phenols after activation as phosphate derivatives (adapted from [81] i ; [82], ii; and [83], iii).
Scheme 28: Synthesis of medium and large-sized nitrogen-containing heterocycles (adapted from [85]).
Scheme 29: Synthesis of arylstannane from aryl phosphate prepared by an AT reaction (adapted from [86]).
Scheme 30: Synthesis and use of aryl dialkyl phosphate for the synthesis of biaryl derivatives (adapted from [89])....
Scheme 31: Synthesis of aryl dialkyl phosphate by an AT reaction from phenol and subsequent rearrangement yiel...
Scheme 32: Selected chiral phosphoramidates used as organocatalyst; i) chiral phosphoramidate used in the pion...
Scheme 33: Determination of ee of H-phosphinate by the application of the AT reaction with a chiral amine (ada...
Scheme 34: Chemical structure of selected flame retardants synthesized by AT reactions; (BDE: polybrominated d...
Scheme 35: Transformation of DOPO (i) and synthesis of polyphosphonate (ii) by the AT reaction (adapted from [117] ...
Scheme 36: Synthesis of lipophosphite (bisoleyl phosphite) and cationic lipophosphoramidate with an AT reactio...
Scheme 37: Use of AT reactions to produce cationic lipids characterized by a trimethylphosphonium, trimethylar...
Scheme 38: Cationic lipid synthesized by the AT reaction illustrating the variation of the structure of the li...
Scheme 39: Helper lipids for nucleic acid delivery synthesized with the AT reaction (adapted from [130]).
Scheme 40: AT reaction used to produce red/ox-sensitive cationic lipids (adapted from [135]).
Scheme 41: Alkyne and azide-functionalized phosphoramidate synthesized by AT reactions,(i); illustration of so...
Scheme 42: Cationic lipids exhibiting bactericidal action – arrows indicate the bond formed by the AT reaction...
Scheme 43: β-Cyclodextrin-based lipophosphoramidates (adapted from [138]).
Scheme 44: Polyphosphate functionalized by an AT reaction (adapted from [139]).
Scheme 45: Synthesis of zwitterionic phosphocholine-bound chitosan (adapted from [142]).
Scheme 46: Synthesis of AZT-based prodrug via an AT reaction (adapted from [143]).
Cyclodextrin-based nanosponges as drug carriers
- Francesco Trotta,
- Marco Zanetti and
- Roberta Cavalli
Beilstein J. Org. Chem. 2012, 8, 2091–2099, doi:10.3762/bjoc.8.235
- encapsulating some important agricultural chemicals. In this case, release is controlled and has a slow profile [27]. Finally, nanosponges can also be used in polymer processing to improve flame-retardant properties [28][29] and in enantio-differentiating photoisomerization reactions [30]. Application of
Graphical Abstract
Scheme 1: Synthetic routes to cyclodextrin nanosponges. (a) Cyclodextrin carbonate nanosponges. (b) Cyclodext...
Figure 1: Molecular structure of cyclodextrin carbonate nanosponges.
Figure 2: TEM microphotograph of cyclodextrin carbonate nanosponge (magnification 46,000×).
Regioselective ester cleavage during the preparation of bisphosphonate methacrylate monomers
- Kamel Chougrani,
- Gilles Niel,
- Bernard Boutevin and
- Ghislain David
Beilstein J. Org. Chem. 2011, 7, 364–368, doi:10.3762/bjoc.7.46
- tested, after copolymerization and incorporation, in a desensitizing solution for lithography [22]. More recently we investigated a similar compound 1a for its adhesive or anticorrosive or flame-retardant properties [20][21]. The synthesis of bisphosphonate monomers 1c–7c is described in Scheme 2. Thus
Graphical Abstract
Scheme 1: Novel bisphosphonate methacrylate monomers.
Scheme 2: Synthesis of novel bisphosphonate methacrylate monomers 1c–7c, by use of the following reagents and...
Scheme 3: Schematic procedure for phosphonate methacrylate monomer deprotection.
