Molecular structure of (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide. Synthesis of (3,5-diallylisocyanuratomethyl)phosphine sulfides

X-Ray study of the (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine oxide showed that the phosphorylmethyl group is bonded to the nitrogen atom of the cycle. Reaction of the tris(chloromethyl)phosphine sulfide with sodium diallylisocyanurate gave (3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide, and treatment of the tris(3,5-diallylisocyanuratomethyl)phosphine oxide with phosphorus pentasulfide gave a tris(3,5-diallylisocyanuratomethyl)bis(chloromethyl)phosphine sulfide.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1446–1448, August, 1993.     

Reactions of Bis(chloromethyl)phosphinic(-Phosphinothioic) Chlorides with Silylated Carbamates and Trimethylsilyl N-Trimethylsilylacetimidoate

Bis(chloromethyl)phosphinic chloride reacts with trimethylsilyl methylcarbamate in benzene in the presence of a base to give trimethylsilyl bis(chloromethyl)phosphinate. The same reaction performed without a solvent and in the absence of a base yields trimethylsilyl bis(chloromethyl)phosphinate and bis(chloromethyl)phosphinic anhydride. Reaction of bis(chloromethyl)phosphinic chloride with trimethylsilyl diethylcarbamate yields N,N-diethylbis(chloromethyl)phosphinic amide. The reaction of bis(chloromethyl)phosphinic (-phosphinothioic) chlorides with trimethylsilyl N-trimethylsilylacetimidoate was studied.     

Synthesis of Bis(phosphinoyl)amines and Phosphinoyl–Phosphorylamines by the N‐Phosphinoylation and N‐Phosphorylation of 1‐Alkylamino‐2,5‐dihydro‐1H‐phosphole 1‐Oxides

The N‐phosphinoylation and N‐phosphorylation reaction of 1‐alkylamino‐2,5‐dihydro‐1H‐phosphole 1‐oxides with diphenylphosphinoyl chloride and diethylphosphoryl chloride/diphenylphosphoryl chloride afforded new families of compounds comprising bis(phosphinoyl)amines and phosphinoyl‐phosphorylamines, respectively, whose stereostructures were elucidated by B3LYP/6‐31G(d,p) and B3LYP/6‐31G++(d,p) calculations. The P analogues of the mixed imides may be valuable intermediates in syntheses.     

2,3-Bis(diphenylphosphino)-1,3-butadien

2,3-Bis(diphenylphosphino)-1,3-butadiene A method for synthesis of the title compound is described, using the readily available 2,3-bis(diphenylphosphinoyl)-1,3-butadiene ( 1 ) as the starting material. For the protection of the diene system, 1 is first converted into the 1,4-dibromo- and 1,4-dichloro derivatives 2a and b , respectively, by addition of Br₂ or Cl₂, respectively. The structure of 2b has been determined by single-crystal X-ray diffraction. The molecule has a centrosymmetrical (E)-configuration. Reduction of the phosphinoyl groups by HSiCl₃(to give the bis(diphenylphosphino)compound 3), followed by removal of the Cl-atoms using Zn powder, affords the bis(diphenylphosphino)butadiene 4 . Compounds 3 and 4 give quaternary phosphonium salts 5 and 6 , respectively, on addition of CH₃OSO₂F or CH₃I. The sulfur analogue of 1 is formed on treatment of 4 with elemental sulfur.     

Synthesis of original benzo[g]quinoxaline‐5,10‐diones by bis‐SRN1 methodology

A new heterocyclic bioreductive bis‐alkylating agent, 2,3‐bis(chloromethyl)benzo[g]quinoxaline‐5,10‐dione, was prepared in a four‐steps synthesis. It was shown to react under electron transfer conditions with 2‐nitropropane anion by an bis‐S_RN1 mechanism to give three C‐alkylation products in excellent yields. Extension of this bis‐S_RN1 reaction to various nitronate or malonate anions and S‐centered anions led to a new class of potentially active benzo[g]quinoxaline‐5,10‐dione derivatives.     

Nitrogen-containing organosilicon compounds

Fifteen previously unknown piperidinosilanes of the type R_4–m Si[(CH₂) _n NC₅H₁₀] _m (m=1–3; n=0–3). have been synthesized by the reaction of piperidine with diethylaminotrimethylsilane, bis(diethylamino)dimethylsilane, chlorobis(dimethylamino)methylsilane, trichloro(methyl)silane, trialkyl(chloromethyl)silanes, dialkoxy(alkyl)(chloromethyl)silanes, trialkylvinylsilanes, trialkyl(3-chloropropyl)silanes, and 3-chloropropyl(diethoxy)methylsilane. The piperidinosilanes (n>0) have been converted into the corresponding hydrochlorides and methiodides.For part VIII, see [1].     

(3,5-Diallylisocyanuratomethyl)phosphine oxides and some of their properties

Reaction of sodium diallylisocyanurate with tris(chloromethyl)-, bis(chloromethyl)phenyl-, and (chloromethyl)diphenylphosphine oxides yields, depending on the stoichiometric ratio of the reagents, mono-, bis-, and tris(3,5-diallylisocyanuratomethyl)phosphine oxides.A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Science Center, Russian Academy of Sciences, 420083 Kazan, Tatarstan, Russia. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 12, pp. 2773–2777, December, 1992.     

Synthesis of poly(cyanurate)s by a novel polyaddition of bis(epoxide)s with triazine dichloride

Poly(cyanurate)s (P‐1–P‐4) containing triazine groups in the main chain and pendant chloromethyl groups in the side chain were synthesized by the polyaddition of bis(epoxide)s with 2,4‐dichloro‐6‐(diphenylamino)‐s‐triazine (DPAT) using quaternary onium salts as catalysts. The polyaddition of diglycidyl ether of bisphenol‐A (DGEBA) with DPAT proceeded smoothly in chlorobenzene at 100 °C for 12 h to give P‐1 with M_n = 19,000 in a 92% yield, when tetrabutylammonium chloride (TBAC) was used as a catalyst. However, no reaction occurred without a catalyst or with triethylamine alone under the same reaction conditions. Polyadditions of other bis(epoxide)s with DPTA also proceeded smoothly using 5 mol % of TBAC as a catalyst in chlorobenzene to produce corresponding polymers (P‐2≈P‐4) in high yields under similar reaction conditions. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4006–4012, 2000     

Aminolysis of P-trichloro-N-dichlorophosphorylmonophosphazene and the crystal structure of 1-(dichlorophosphinyl)-2-chloro-2,2-bis(diisopropylamino)phosphazene

The reactions of Cl₃PN P(O)Cl₂ ( 1 ) with primary and secondary amines have been studied. The following monophosphazenes, (RRN)₃PN P(O)(NRR)₂, and bis(phosphinoyl)amines, [(RRN)₂P(O)]₂NH were isolated: NRR = NHCH₂Ph, Net₂, NH(CH₂)₂CH₃ groups for monophosphazenes, and Net₂, NH(CH₂)₂CH₃ for phosphinoyl amines. The unexpected geminal phosphazene, Cl(RRN)₂PN P(O)Cl₂, {RRN = N[CH(CH₃)₂]₂}, was also obtained in moderate yield. The spectral data (IR, ¹H, ¹³C, and ³¹P NMR, and MS) are presented. The structure of 1-(dichlorophosphinyl)-2-chloro-2,2-bis(diisopropylamino)phosphazene ( 5 ) was determined by X-ray crystallography. The basicities of these and related compounds in nonaqueous nitrobenzene solution were obtained by potentiometric titration.     

Synthesis and characterization of poly(3,3 bis(azidomethyl)oxetane‐co‐ε‐caprolactone)s

The quasi‐living cationic copolymerization of 3,3‐bis(chloromethyl)oxetane (BCMO) and ε‐caprolactone (ε‐CL), using boron trifluoride etherate as catalyst and 1,4‐butanediol as coinitiator, was investigated in methylene chloride at 0°C. The resulting hydroxyl‐ended copolymers exhibit a narrow molecular weight polydispersity and a functionality of about 2. The reactivity ratios of BCMO (0.26) and ε‐CL (0.47), and the T_g of the copolymers, indicate their statistical character. The synthesis of poly(3,3‐bis(azidomethyl)oxetane‐co‐ε‐caprolactone) from poly(BCMO‐co‐ε‐CL) via the substitution of the chlorine atoms by azide groups, using sodium azide in DMSO at 110°C, occurs without any degradation, but the copolymers decompose at about 240°C. All polymers were characterized by vapor pressure osmometry or steric exclusion chromatography, ¹H‐NMR and FTIR spectroscopies, and DSC. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1027–1039, 1999     

Syntheses and properties of tetraaza‐, diaza‐, tetraoxa‐, and dioxa‐metacyclophanes

Metacyclophanes were prepared by cyclization reactions between bis(chloromethyl) compounds and piperazine, primary amines, or ethylene glycol. The ¹H nmr relaxation time (T₁) measurements indicated that the macrocycles feature the up and down motion of the aromatic units around the XCH₂Ar (X = N, O) methylene moieties as the axes. Metacyclophanes incorporating piperazine units showed high complexation ability for alkaline metal cations.     

A Convenient Preparation of Fluorinating Reagent F‐TEDA Bearing Bisphenylsulfonylimide Counterion and Its Fluorination to Oxindoles

The direct preparation of a kind of fluorinating reagent 1 [F‐TEDA‐N(SO₂Ph)₂] was realized in high yield via the complexation of N‐fluorobenzenesulfonimide (NFSI) with 1‐(chloromethyl)‐1,4‐diazabicyclo[2.2.2]octan‐1‐ium N′,N′‐bis‐(benzenesulfonylimide) salt. In its fluorination to oxindoles, the fluorinating products 6 were afforded in moderate to high yields.     

2,3- and 3,4-Bis(diethoxyphosphorylmethyl)-5-tert-butylfurans

Reduction of 2-, 4-acetoxymethyl derivatives of 5-tert-butylfuran-3-carboxylic acid leads to the corresponding bis(hydroxymethyl)furans. Bis(chloromethyl)furans prepared from the latter were involvedin reaction with sodium diethyl phosphite. In the presence of two equivalents of a phosphorus-containing nucleophile, bis(phosphonomethyl)furans are formed. One equivalent of sodium diethyl phosphite reacts with 3,4-bis(chloromethyl)furan to give a mixture of 3-and 4-phosphorylated products in a 4.5:1 ratio in a low yield. The revealed difference in reactivity between the 3- and 4-chloromethyl groups demonstrates the importance of shielding of the chloromethyl group by the neighboring tert-butyl substituent. Examination of the ¹H NMR spectra of 3,4-bis(hydroxymethyl)-, 3,4-bis(chloromethyl)-, 3,4-bis(diethoxyphosphorylmethyl)-5-tert-butylfurans, and also specially prepared 5-tert-butyl-3-(diethoxyphosphorylmethyl)-4-(ethoxymethyl)-2-methylfuran established that the signal of the substituent neighboring to the tert-butyl group is always shifted downfield.     

(2S,4S,SFc)-2-[2-(Diphenyl­thio­phosphinoyl)­ferrocenyl]-4-methoxy­methyl-1,3-dioxane

The title compound, [Fe(C₅H₅)(C₂₃H₂₄O₃PS)], is a very useful inter­mediate for the synthesis of enanti­omerically pure (S)-2-[(diphenyl­thio­phosphinoyl)ferrocenyl]methanol or (S)-2-(diphenyl­thio­phosphinoyl)ferrocene­carboxaldehyde. The dioxane ring has a chair conformation and is twisted with respect to the cyclo­penta­dienyl ring to which it is attached. There is an inter­molecular C—H⋯O hydrogen-bonding inter­action which links the mol­ecules into C(8) chains developing parallel to the a axis. Owing to this weak inter­action, the two cyclo­penta­dienyl rings are twisted with respect to each other by 16.0 (3)°, and so have a conformation which might be regarded as inter­mediate between eclipsed and staggered. The absolute configuration deduced from the X-ray analysis fully confirms the sterochemistry expected from the chemical pathway.     

Functional derivatives of (bromomethyl)phosphonic acid

Reaction of equimolar amounts of (bromomethyl)phosphonic dichloride and phenol gives phenyl (bromomethyl)chlorophosphonate. Its reactions with heptamethyldisilazane, N,O-bis(trimethylsilyl)acetamide, and potassium thiocyanate, leading respectively to a silylamidophosphonate, a silyl phosphonate, and an isothiocyanatophosphonate, were studied. (Bromomethyl)(chloromethyl)phosphinoyl isocyanate was synthesized. Chemical properties of the prepared functionalyzed (bromomethyl)phosphonates were investigated.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 8, 2004, pp. 1262–1265.Original Russian Text Copyright © 2004 by Kibardina, M. Pudovik, Kamalov, and A. Pudovik.This revised version was published online in April 2005 with a corrected cover date.     

Synthesis, molecular and crystal structure, and features of the electronic structure of bis(O’i)-chelated bis(2,2-dimethylbenzo-[2H]-4-oxo-1,3-oxazino-3-methyl)difluorosilane

A method has been developed for the synthesis of a bis(O→Si)-chelated bis(2,2-dimethylbenzo[2H]-4-oxo-1,3-oxazino-3-methyl)difluorosilane from 2,2-dimethyl-3-trimethylsilylbenzo[2H]-1,3-oxazin-4-one and bis(chloromethyl)dichlorosilane via the intermediate formation of the corresponding unstable bis-chelated dichloride, subsequent hydrolysis with NaHCO₃ and, without separation, treatment of the hydrolysis product with boron trifluoride etherate. Analysis of the electron density distribution showed the presence of dative bonding in both O→Si-F fragments. Dedicated to Prof. Edmunds Lukevics on the occasion of his 70th birthday __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1866–1879, December, 2006.     

Synthesis and transformations of acyloxy(chloromethyl)phosphonates and acyloxy(chloromethyl)phosphinates

The reactions ofO-phenyl chloromethylphosphonochloridate and bis(chloromethyl)phosphinous chloride with sodium acetate afford the corresponding acyloxyphosphonates and acyloxyphosphinates, which are readily transformed due to disproportionation into pyrophosphonates and pyrophosphinates. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp 2383–2385, November, 1998.     

Synthesis and properties of poly(oxyethylene)s containing thioether,sulfoxide, or sulfone groups

Poly[oxy(ethylthiomethyl)ethylene] (ETE) was prepared from poly[oxy (chloromethyl)ethylene] (CE) by reaction with sodium ethanethiolate. Sulfoxide and sulfone analogues were synthesized by oxidation of the poly[oxy(ethylthiomethyl)ethylene]. By changing the chloromethyl/sodium ethanethiolate ratio, poly[oxy (chloromethyl)ethylene-co-oxy(ethylthiomethyl)ethylene] (CE-ETEs) were easily made. Poly[oxy(ethylsulfinylmethyl)ethylene] (ESXE), poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfinylmethyl)ethylene] (CE-ESXEs), poly[oxy(ethylsulfonylmethyl)ethylene] (ESE), and poly[oxy(chloromethyl)ethylene-co-oxy(ethylsulfonylmethyl)ethylene] (CE-ESEs) were obtained by oxidation of ETE or CE-ETEs. There was little if any chain degradation. The (co)polymer structures were confirmed by FTIR and ¹H-NMR spectroscopic studies. Their thermal properties were studied by DSC and TGA. T_gs of ETE, ESXE, and ESE were -57, 36, and 57°C, respectively, and T_d,os (initial decomposition temperature, TGA) were 331, 198, and 308°C, respectively. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 793–801, 1998     

New trigonal tris(phosphine oxides)

The reaction of 1,1,1-tris(chloromethyl)propane with diphenylphosphine under phase-transfer conditions afforded 1,1,1-tris(diphenylphosphinomethyl)propane, whose oxidation gave a previously unknown representative of trigonal tris(phosphine oxides), viz., stable 1,1,1-tris(diphenylphosphorylmethyl)propane. Its analogs, viz., bis(diphenylphosphoryl)diphenylphosphinomethane and tris(diphenylphosphoryl)methane, are unstable in air and decompose with the cleavage of the P-C bond.Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1926–1929, September, 2004.     

Synthesis and catalytic activity of novel xylyl‐linked benzimidazolium salts

The reaction of 1‐alkylbenzimidazole derivatives with o‐/p‐di(chloromethyl)benzene results in the formation of the new o‐/p‐xylyl‐linked bis(benzimidazolium) salts, 1 and 2, respectively. The salts were characterized by NMR spectroscopy and elemental analysis. The in situ prepared complexes derived from Pd(OAc)₂–1 and 2 exhibit catalytic activity (61–98%), to give the Heck coupling products of aryl bromides and styrene. Copyright © 2009 John Wiley & Sons, Ltd.