- Photochemical Rearrangement of Dialkylphosphinic Azides in Methanol and Other Protic Solvents
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On photolysis in methanol di-t-butylphosphinic azide (4; R=But) rearranges with loss of nitrogen to give methyl NP-di-t-butylphosphonamidate (6; R=But, X=OMe) (71percent), presumably by way of a monomeric metaphosphonimidate (5; R=But) which is trapped by the solvent.Analogous rearrangements occur in other alkohols and in t-butylamine, althogh di-t-butylphosphinic amide is also a substantial product in ethanol and the major product in isopropyl alcohol.Di-isopropylphosphinic azide (4; R=Pri) behaves in a similar way, but in methanol the less hindered diethylphosphinic azide (4; R=Et) suffers extensive solvolysis to methyl diethylphosphinate.
- Harger, Martin J. P.,Stephen, Michael A.
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- Reactions of Benzylidene Chlorides with S-Methyl Diethylphosphinothioate
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S-Methyl diethylphosphinothioate reacted with benzylidene chlorides to give the corresponding aryl(chloro)methyl methyl sulfide and diethylphosphinoyl chloride. The product structure suggests initial attack of the methylsulfanyl group on the CH carbon ato
- Gazizov,Valieva,Ivanova, S. Yu.,Karimova,Khairullin,Gazizova
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- Mono- and Di(dechloromethylthioylation) of Dichloromethylarenes with S-Methyl Diethylthiophosphinate
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Abstract: The attack of the thiol sulfur atom (P–SMe) on the methine carbon as the main route of the new reaction of dichloromethylarenes with S-methyl diethylthiophosphinate has been predicted and experimentally confirmed on the basis of the electronic s
- Gazizov,Valieva,Ivanova, S. Yu.,Khairullin,Kirillina, Yu. S.,Antipin
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- S-Methyl diethylthiophosphinate in mono- and di(dechloromethylthioylation) of substituted benzylidene chlorides
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The main route of a new reaction of (dichloromethyl)arenes with S-methyl diethylthiophosphinate is the attack of the thiol sulfur atom (P–SMe) on the methylene carbon atom. A new method for synthesizing dimethyl dithioacetals of arenecarbaldehydes without
- Gazizov,Valieva,Ivanova, S. Yu.,Khairullin,Kirillina, Yu. S.,Khairullina,Ibragimov, Sh. N.
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- Preparation method of dialkyl phosphinate
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The invention discloses a preparation method of dialkyl phosphinate, which comprises the following steps: using dialkyl phosphinate and a halogenated compound as raw materials, reacting under the action of a catalyst to obtain dialkyl phosphinate; the catalyst is one or more of a phase transfer catalyst or an amphoteric compound, and comprises at least one of a cationic polyalkyl quaternary ammonium salt compound, a cationic halogenated polyalkyl quaternary ammonium salt compound, alkyl ammonium chloride, alkyl ammonium bromide, an anionic alkyl sulfate compound, alkyl sulfonate, alkylbenzene sulfonate, a nonionic surfactant and quaternary phosphonium salt. The dialkyl phosphinate is synthesized by adopting the dialkyl phosphinate and the halogenated compound as raw materials through a one-step method, and compared with an existing traditional synthesis method, the invention has the advantages that the yield is higher, byproducts are few, separation is easy, the steps are simple, consumed time is short, the process is safe and environmentally friendly, the cost is low, and implementation is easier.
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Paragraph 0055; 0059-0060
(2021/04/17)
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- The brush of a motor tooth
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A cleaning section (10; 110) of an electrical toothbrush having a motor and a drive shaft, the cleaning section (10; 110) comprising a movable bristle holder (26; 126) structured to receive a drive motion from the motor via the drive shaft having a longitudinal axis, wherein the drive shaft is structured to oscillate around its longitudinal axis a head (22; 122) including a first plurality of cleaning bristles (24; 124) arranged in a static bristle field and a second plurality of cleaning bristles (28; 128) supported within the movable bristle holder to have at least one freedom of motion relative to the first plurality of cleaning bristles, wherein the movable bristle holder (26; 126) is movable with respect to the head and the static bristle field such that a cleaning motion of the second plurality of bristles includes an oscillating movement relative to the first plurality of cleaning bristles, and wherein the oscillating movement of the second plurality of bristles is caused by the oscillating movement of the drive shaft, and wherein the head further includes an opening (42; 142) sized to receive the movable bristle holder (26; 126) therein.
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- N-(Dialkylphosphinoyl)hydroxylamines : Preparation using N,O-Bis(trimethylsilyl)hydroxylamine and Migration of Simple Alkyl Groups in the Rearrangements of their O-p-Nitrobenzenesulphonates
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Treatment of Pri2P(O)Cl with Me3SiNHOSiMe3 gives Pri2P(O)NHOSiMe3, which is desilylated by methanol giving Pri2P(O)NHOH.The O-p-nitrobenzenesulphonyl derivative of this rearranges with KOBut in ButOH, an isopropyl group migrating from P to N and the phosphonamidate PriP(O)(OBut)NHPri being formed quantitatively.Rearrangement also occurs in other alcohols (MeOH, EtOH, PriOH), but not quite as cleanly.In ButNH2 the phosphinoylhydrazine Pri2P(O)NHNHBut is formed as well as the rearrangement product, PriP(O)(NHBut)NHPri.The p-nitrobenzenesulphonyl derivatives of Et2P(O)NHOH and PriMeP(O)NHOH, prepared similarly with Me3SiNHOSiMe3, also rearrange quantitatively with ButOH - KOBut.In the latter case, the migratory aptitudes of the two alkyl groups (Pri and Me) are almost identical.
- Harger, Martin J. P.,Shimmin, P. Andrew
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p. 7539 - 7550
(2007/10/02)
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- SYNTHESIS AND CHEMISTRY OF DIALKYL- AND DIARYLTRICHLOROMETHYLPHOSPHINES
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Dialkyltrichloromethylphosphines; diphenyltrichloro-methylphosphine; P-chloro-dialkyl-dichloromethylenephosphoranes; P-chloro-diphenyl-dichloromethylenephophorane; phosphonium salt; chlorination; dehydration; condensation.
- Majewski, Piotr
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p. 185 - 194
(2007/10/02)
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- SOLVOLYSIS OF CHLORODIALKYL- AND DIARYLPHOSPHINES, DIALKYL PHOSPHOROCHLORIDITES AND DIALKYL PHOSPHINYL CHLORIDES
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The kinetics of solvolysis of chlorodiethylphosphine, chloro(di-n-propyl)phosphine and chlorodiphenylphosphine was studied by conductometry in pure ethanol and in various mixed solvents, and was compared with that of dialkyl phosphorochloridites and of dialkyl and diaryl phosphinyl chlorides.The rate of ethanolysis of chloro(di-n-propyl)phosphine was found to be larger at higher initial concentrations.Addition of sulfuric or perchloric acid enhanced the rate of solvolysis, while sodium perchlorate and lithium chloride had no influence.In ethanol containing water, the rate of solvolysis of chloro(di-n-propyl)phosphine is approximately proportional to the concentration of water.In formic acid, the solvolysis of chloro(di-n-propyl)phosphine is slower than in ethanol.Addition of acetone to ethanol increases the rate of solvolysis of chloro(di-n-propyl)phosphine - possibly due to a condensation reaction producing a 1-chloroalkyl dialkylphosphine oxide.The rate of ethanolysis of chloro(di-n-propyl)phosphine is considerably enhanced in the presence of isobutylamine, di-n-butylamine and triethylamine.The solvolysis of di-t-butylphosphinyl chloride in absolute ethanol is very much slower than that of dimethyl and diethyl phosphinyl chloride.Key words: Solvolysis; chlorodialkylphosphines; chlorodiphenylphosphine; dialkyl phosphorochloridite; dialkylphosphinyl chlorides; acid catalysis.
- Halmann, M.
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p. 251 - 262
(2007/10/02)
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- INVESTIGATION OF THE REACTION BETWEEN DIALKYLPHOSPHINE OXIDES AND CARBONTETRACHLORIDE
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The time dependent formation of intermediates and end products in the reaction between Et2P(O)H and CCl4 is analysed using (31)P-NMR technique.The various reaction steps are studied separately in order to elucidate the overall mechanism.A key step is the disproportionation of Et2P(O)H catalysed by Et2PCl and Et2P(O)Cl, in a cyclic process, the latter being produced initially by the reaction between Et2P(O)H and CCl4.The diethylphosphine formed during disproportionation reacts immediately with CCl4, driving the reaction through the intermediates, Et2PCl and Et2PCCl3which react with Et2P(O)OH producing Et2P(O)Cl, (Et2PO)2O, and Et2P(O)CHCl2, as end products.The influence of the substituents on rate and product yields was studied with n-propyl, n-butyl, n-octyl, and allyl as substituents in the dialkylphosphine oxide.
- Aksnes, Gunnar,Majewski, Piotr
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p. 261 - 274
(2007/10/02)
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- Amino acid derivatives and antihypertensive drugs containing them
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N-terminal phosphorus dipeptides having antihypertensive properties are disclosed.
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- PHOSPHORIC, PHOSPHONIC, AND PHOSPHINIC ACID AMIDES AS BASES
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Potentiometric titration in nitromethane, IR- and NMR-spectroscopy were used to study the processes of protonation and H-bonding for a number of phosphoric, phosphonic and phosphinic acid amides. 12N)nP(O)R23-n(R1=Me, Et; R2=EtO, Me, Et; n=1-3) including 1,3,2-dioxa-, 1,3,2-oxazaphospholane and phosphorinane derivatives>.It was shown that in these compounds the center of the highest basicity is the oxygen of the phosphoryl group.
- Matrosov, E. I.,Kryuchkov, E. E.,Nifantyev, E. E.,Kozachenko, A. G.,Kabachnik, M. I.
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