- MATERIALS FOR ORGANIC ELECTROLUMINESCENT DEVICES
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The present invention relates to compounds of the formula (1) which are suitable for use in electronic devices, in particular organic electroluminescent devices, and to electronic devices, which comprise these compounds.
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Page/Page column 61
(2018/06/06)
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- Selective Substitution of POCl 3 with Organometallic Reagents: Synthesis of Phosphinates and Phosphonates
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The selectivity of the substitution reaction of phosphoryl chloride with organometallic reagents was investigated using NMR spectroscopy. This led to the discovery that the selectivity of the substitution reaction can be tuned by choosing a proper organometallic reagent. A phosphinate could be obtained by using a Grignard reagent whereas an organozinc reagent provided a phosphonate. Based on these results, one-pot synthetic methods for the preparation of phosphinates and phosphonates using commercially available starting materials were developed. Both methods allow the synthesis of a broad range of either phosphinate or phosphonate derivatives in a straightforward and general procedure. Moreover, using these one-pot procedures, mixed systems substituted with different alkyl/aryl groups can be prepared.
- Verbelen, Bram,Dehaen, Wim,Binnemans, Koen
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p. 2019 - 2026
(2018/04/14)
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- New method for synthesizing substituted phosphinate
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The invention discloses a new method for synthesizing substituted phosphinate. The method comprises the step of generating the substituted phosphinate by reducing halogenated phosphonate under the effect of a reducing agent. The optimal preparation method for the substituted phosphinate is screened through a large number of experiments according to the invention; the whole process is reasonably designed; the technological operation is simple and efficient; especially, the optimal reaction conditions are screened, including reaction solvent, reaction temperature, reaction time and optimal reaction pH value; the reaction yield is obviously increased; the yield reaches up to 85-95%; the side reaction is less; the production cost is greatly lowered; the industrial production can be realized; and the method has a wide application prospect.
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Paragraph 0032-0034
(2017/12/27)
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- Cyclic Phosphine Oxides and Phosphinamides from Di-Grignard Reagents and Phosphonic Dichlorides: Modular Access to Annulated Phospholanes
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The reaction between 1,4-di-Grignard reagents and phosphonous(III) dichlorides is a classical method for the direct synthesis of phospholanes. Reported here is an extension of this approach to the preparation of value-added, annulated phospholane oxides, achieved through the combination of carbocyclic-fused di-Grignard reagents and readily available phosphonic(V) dichlorides. The procedure is amenable to (benz)annulation at both the 2,3- and 3,4-positions of the phospholane ring, and a variety of aliphatic, cyclic and aryl P-electrophiles are tolerated in reasonable to excellent yields.
- Gregson, Aaron M.,Wales, Steven M.,Bailey, Stephen J.,Willis, Anthony C.,Keller, Paul A.
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p. 9774 - 9780
(2015/10/12)
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- Anti-cocaine catalytic antibody
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Disclosed are catalytic antibodies and polypeptides capable of degrading cocaine. Said catalytic antibodies and polypeptides are characterized by the amino acid sequence of their complementary determining regions and framework regions. The present invention also discloses a pharmaceutical composition and a method for decreasing the concentration and a method for decreasing the concentration of cocaine of a subject. Finally, the invention discloses pharmaceutical compositions and methods for treating cocaine overdose and addiction in subjects.
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- The mechanism of thionyl chloride reaction with dialkyl alkylphosphonothionate using 31P NMR
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Based on 31P NMR studies of thionyl chloride reaction with dialkyl alkylphosphonothionates, a method for preparation of alkylphosphonic dichloride has been investigated. A mechanism via intermediacy of ester chloride is suggested.
- Purnanand,Shakya,Saxena, Shefali,Sharma,Lal, Basant
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p. 1093 - 1099
(2007/10/03)
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- Studies on chiral thiophosphoric acids and their derivatives 16. - The asymmetric cyclization of L-(+)-prolinol with (thio)phosphoro(-no)dichloridates
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The cyclizations of L-(+)-prolinol 5 with (thio)phosphoro(-no)dichloridates 6 give 1,2,3-azaphosphaoxabicyclo[3.3.0]octanes 7 consisting of unequal amounts of diastereoisomers, eight pairs of which have been successfully resolved by silica gel column chromatography or recrystallization. The influences of reaction temperature, solvent and substrate concentration upon the asymmetric induction have also been investigated.
- He, Zheng-Jie,Wang, You-Ming,Tang, Chu-Chi
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- Reactions of aryltetrachlorophosphoranes with sodium dithionite and sulfuryl chloride
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Reaction of aryltetrachlorophosphoranes with sodium dithionite or sulfuryl chloride leads to dichloroanhydrides of arylphosphonic acids in high yields. 1996 MAEe cyrillic signK Hayκa/Interperiodica Publishing.
- Mitrasov,Anisimova,Kormachev
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p. 765 - 766
(2007/10/03)
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- A general synthesis of phosphonic acid dichlorides using oxalyl chloride and DMF catalysis
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A general synthesis of phosphonic diacid dichlorides (1) using oxalyl chloride and catalytic DMF is described.
- Rogers, Roland S.
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p. 7473 - 7474
(2007/10/02)
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- CONVERSIONS OF THE ADDUCTS OF α-DICHLORONITROSOALKANES WITH DICHLOROPHOSPHINES
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Structure, stability and some reactions of the obtained adducts of α-dichloronitrosoalkanes with dichlorophosphines are discussed.One-pot synthesis of O-(alkylchloroformoimino)phosphonic acid chlorides and esters is described.Key words: O-(alkylchloroformoimino)trichlorophosphoranes; O-(alkylchloroformoimino)chlorophosphonates; O-(alkylchloroformoimino)-O-alkylphosphonates; amides of O-(alkylchloroformoimino)phenylphosphonic acids.
- Lyashenko, Yu. E.,Sokolov, V. B.,Martynov, I. V.
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- 4-Substituted 1,3,5,7-Tetramethyl-1,3,5,7-tetraza-4λ5-phosphaspiroheptane-2,6-diones; Crystal Structure of 1,3,4,6,7,9,10-Heptamethyl-5-oxa-1,3,7,9,10-pentaaza-4λ5,6λ5-diphosphadispirodecane-2,8-dione
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The reaction of the tetrachlorophosphoranes RPCl4 (R=Me, Ph) with N,N'-dimethylurea (dmh) (1), or of the diazaphosphetidinone O=C(NMe)2PR (R=CCl3) (3) and chlorine with N,N'-bis(trimethylsilyl)-N,N'-dimethylurea (2) furnished the spiro compounds RP2 (7-9).The dichlorophosphoranes O=C(NMe)2PRCl2 (4-6) are intermediates in these reactions; 4 and 6 were isolated but 5 could not be obtained pure.In the reaction of 4 with 2 a mixture of products was formed, from which the novel tricyclic diphosphorane 1,3,4,6,7,9,10-heptamethyl-5-oxa-1,3,7,9,10-pentaaza-4l5,6λ5-diphosphadispirodecane-2,8-dione (10) was isolated in low yield.Its identity and structure were established by 1H, 13C and 31P NMR spectroscopy and by a single crystal X-ray structure determination, which confirmed the presence of the novel oxazadiphosphetidine ring. 10 crystallizes in C2/c with a=1321.1(3), b=687.6(1), c=1674.5(3) pm, β=103.30(2) deg and Z=4; R=0.039 for 1437 unique observed reflections.A crystallographic twofold axis passes through the Me-N...O moiety of the central ring.
- Breker, Johannes,Jones, Peter G.,Schmutzler, Reinhard
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p. 1407 - 1415
(2007/10/02)
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- ORGANIC PHOSPHORUS COMPOUNDS 90. A CONVENIENT, ONE-STEP SYNTHESIS OF ALKYL- AND ARYLPHOSPHONYL DICHLORIDES
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N,N-Disubstituted formamides such as dimethylformamide, N-formylpyrrolidine, N-formylpiperidine etc. and also pyridine and hexamethylphosphonic acid triamide catalyze the chlorination of phosphonates with thionyl chloride to give phosphonyl dichlorides in high yield.Thus RP(O)Cl2, R=CH3, C2H5, n-C12H25, C6H5, have been isolated in better than 90 per cent yield.The procedure is less satisfactory for the production of 2-chloroethylphosphonyl dichloride.Only a 34 per cent yield was realized.The chlorination proceeds very likely through the intermediate formation of the halfesters, RP(O)(OR)Cl since these could be isolated under favorable circumstances.
- Maier, Ludwig
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p. 465 - 470
(2007/10/02)
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- Process of converting a carboxylic acid or carboxylic acid halide group to a trihalomethyl group
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Carboxylic acid or carboxylic acid halide groups on aryl or heterocyclic aryl rings are directly converted to trihalomethyl groups by using a phenylhalophosphorane, optionally generated in situ by reaction of a phenylphosphonous halide and chlorine.
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- SILYLPEROXIDES AS SELECTIVE OXYGENATION REAGENTS IN PHOSPHORUS CHEMISRTY
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Bis(trimethylsilyl)peroxide (BSPO) can be used for chemo- and stereoselective generation of P=O group by oxygenation of P(III) centre and transformation of P=S and P=Se groups.
- Kowalski, Jozef,Wozniak, Lucyna,Chojnowski, Julian
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p. 125 - 128
(2007/10/02)
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- Three-membered Heterocycles,10. - Phosphonohydrazidic Esters by Alkoxide-induced Rearrangement of N-Chlorophosphonic Diamides
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Phosphoric and phosphonic amides 8 are formed from phosphoric and phosphonic chlorides 6 and primary amines 7 in high yields. 2,5-Dimethyl-2,5-hexanediamine (7e) reacts with phenylphosphonic dichloride (6c) to give the perhydro-1,3,2-diazaphosphepine 8h.The amides 8 are converted almost quantitatively into the N-chlorophosphoric and N-chlorophosphonic amides 9 by means of tert-butyl hypochlorite.The N,N'-di-tert-alkyl-N-chlorophosphonic diamides 9 derived from methyl-, tert-butyl-, or phenylphosphonic acid react with methoxide or tertiary alkoxides to afford the phosphonohydrazidic esters 10-13.The methyl ester 10d is also formed from 1,2,3-tri-tert-butyldiazaphosphiridine 3-oxide (14) and methanol. 1H-, 13C-, and 31P-NMR spectra prove that the sharply melting phosphonohydrazidic esters 10-13 exist in solution as two diastereomers with ratios ranging from 9:1 to 6:4.The hydrazidic methyl ester 10d which was investigated as a representative example exhibits a temperature dependent 1H-NMR spectrum.Due to the presence of the tert-alkyl groups, inversion at the tertiary nitrogen atom is slow on each NMR time scale. The independence of the IR spectrum on the concentration shows that the predominant diastereomer of 10d is stabilized by an intramolecular hydrogen bond.The electron impact induced decomposition of the amides 8, N-chloroamides 9, and phosphonohydrazidic esters 10-13 ultimately produces cations which are derived from monomeric metaphosphoric or metaphosphonic acid. 6 N hydrochloric acid first splits off the P-N-tert-butyl group of the methyl ester 10d to give the intermediate 15 which can be isolated or which undergoes further hydrolysis to tert-butylphosphonic acid (17) and tert-butylhydrazine(19).The tert-butyl ester 11d yields the same final products in hot hydrochloric acid.At low temperatures and short reaction times, however, di-tert-butylhydrazine (18) is formed.
- Quast, Helmut,Heuschmann, Manfred,Abdel-Rahman, Mohamed O.
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p. 943 - 966
(2007/10/02)
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- Reactivity and Mechanism of Hydrolysis of Phosphonamides
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The rates of hydrolysis of three phosphonamides, N,N-dimethylphenylphosphonamide (XII), N-(phenylphosphonyl)pyrrolidine (XIII), and N-(phenylphosphonyl)morpholine (XIV), have been investigated.There is firs-order dependence on acidity in the pH range 4-7 with a pH independent region at low pHs, consistent with saturation due to complete formation of the neutral amide.The specific rate constant (k2) and the acidity constant (Ka) were obtained from the dependence of pseudo-first-order rate constants on +>; k2 is 1.27*10-2 s-1 and 1.42*10-3 s-1 and pKa is 4.8 and 5.3 for XII and XII, respectively.The small value of the acidity constants is consistent with predominant N-protonation.The activation parameters for XII are ΔH = 11.1 kcal/mol, ΔG = 20.35 kcal/mol, and ΔS 0 -31 eu.Solvent and salt effects on the rate of hydrolysis of XII are insignificant.The solvent isotope effect, k2(H2O)/K2(D2O), is 1.2 and Ka(H2O)/Ka(D2O) is 3.2.Fluoride ion catalyzed the rate of reaction of XII.The Broensted β value is about -1, implying rate-determining breakage of the P-N bond.The results appear to be most consistent with an SN2(P) mechanism.The reactivity of phosphorus amides is discussed in terms of their structure.
- Rahil, Jubrail,Haake, Paul
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p. 1723 - 1734
(2007/10/02)
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- Process for producing phosphonic acid halides
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Phosphonic acid halides are prepared by reacting a dialkylphosponate with thionyl chloride or thionyl bromide in the presence of a nitrogen compound from the group comprising N,N-disubstituted formamides, tertiary amines and N,N-disubstituted phosphoric acid triamides. Phosphonic acid dihalides as well as phosphonic acid alkylester monohalides can be prepared by the new process.
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- Process for preparing alkyl or aryl phosphorus halides and mixed isomers thereof
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Alkyl or aryl phosphonic or phosphonothioic dihalides and phosphinic or phosphinothioic monohalides are prepared by reacting an alkyl halide or aryl halide respectively with a tri-valent phosphorus compound having at least two halogens attached thereto, and preferably three two halogens such as phosphorus trihalide, in the presence of P4 O10 or P4 S10 under at least autogenous pressure at a temperature of from 200° C. to 450° C. The compounds obtained are useful as constituents in insecticides, fungicides, pharmaceuticals, and as intermediates in preparation of other organophosphorus compounds.
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- Process for the preparation of phosphonic acid dihalides
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A process for the preparation of phosphonic acid dihalides of the formula EQU1 IN WHICH R is α, β-unsaturated alkyl, α, β-unsaturated alkyl, phenyl or benzyl and may be further substituted, which comprises reacting corresponding phosphonic or pyrophosphonic acids or their functional derivatives with acid halides of the formula (CO)n Hal2 where n is 1 or 2.
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- Process for the preparation of phosphonic acid dihalides
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Process for preparing phosphonic acid dihalides of the formula EQU1 wherein R is alkyl of 1 to 18 carbon atoms, cycloalkyl of 4 to 8 carbon atoms, alkenyl of 2 to 18 carbon atoms, phenyl, phenalkyl or alkyl-phenyl of 7 to 8 carbon atoms, phenyl, phenalkyl or alkyl-phenyl of 7 to 8 carbon atoms, all radicals R optionally being substituted by chlorine, bromine, cyano or lower acyloxy, and wherein X is halogen such as 2-chloroethane phosphonic acid dichloride, by reacting phosphonic or thio-phosphonic acids of the formula EQU2 wherein Y is oxygen or sulfur, their salts or functional derivatives, with acid halides of the formula wherein X is chlorine or bromine and n is 1 or 2, in the presence of 0.2 - 5% or in the presence of 0.01 to 0.2% by weight of 1. compounds containing at least one tri- to pentavalent nitrogen or phosphorus atom, which in the case of nitrogen is bound with 1 to 4, in the case of phosphorus with at least 3 valences to organic radicals having up to 20 carbon atoms, two of these valences optionally forming a double bond, or 2. mono-di- or tribasic organic or inorganic fully amidated acids or tri- or pentavalent phosphorus, the N atom of which optionally being substituted by aliphatic radicals having up to 20 carbon atoms, and the organic radicals of which contain up to 20 carbon atoms, If required, in the presence of an inert solvent.
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- Phosphonate polymers
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Novel thermoplastic polymers are provided by the interaction of bis(2-hydroxyethyl) terephthalate and a phosphonyl dihalide.
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