The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylene...The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557（16）, b = 11.299（12）, c = 12.163（13）A,β = 98.707（19）^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ（MoKa） = 0.447 mm^-1, Mr = 388.41, V = 1977（4）A3, F（000） = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.展开更多
The phospha-Wittig(phosphanylphosphinidene titanium(IV)complex)and phospha-Peterson(lithiated diphosphane)reactions were used to obtain phosphanylphosphaalkenes with the general formula XYCvP-PtBu_(2)(X=alkyl or aryl ...The phospha-Wittig(phosphanylphosphinidene titanium(IV)complex)and phospha-Peterson(lithiated diphosphane)reactions were used to obtain phosphanylphosphaalkenes with the general formula XYCvP-PtBu_(2)(X=alkyl or aryl group or H;Y=alkyl or aryl group).Therefore,two series of reactions with different ketones and aldehydes were performed.Examination revealed that the two methods are complementary.For smaller carbonyl compounds,the phospha-Wittig reaction was shown to be a much better method,while for larger substituents(mainly aromatic),the phospha-Peterson reaction was shown to be a reliable method.These studies led to,among other things,the isolation of seven phosphanylphosphaalkenes in crystalline form after the phospha-Peterson reaction:(Ph)_(2)CvP-PtBu_(2)(3a),Z-(Ph)(4-CN-Ph)CvP-PtBu_(2)(3c),(4-CN-Ph)_(2)CvP-PtBu_(2)(3d),(4-MeO-Ph)_(2)CvP-PtBu_(2)(3e),E-tBu(Ph)CvP-PtBu_(2)(3f),E-{(Me)_(2)N-Ph}(H)CvP-PtBu_(2)(4d)and E-PhPh(H)CvP-PtBu_(2)(4e).The corresponding compounds were obtained in high yields under mild conditions,and more importantly,these new species are relatively air-and absolutely moisture-stable,especially those originating from aldehydes.In addition,a comprehensive DFT study helped us to establish not only the key factors crucial for effective phospha-Wittig-based synthesis of CvP-P species but also the consecutive steps along the reaction path leading to the formation of these compounds.展开更多
基金This work was supported by the China Petroleum & Chemical Science and Technology Foundation (No. 205026) the Tianjin Science and Technology Plan Foundation (No. 06TXTJJC14400)
文摘The title compound N,N＇-bis（5,5-dimethyl-2-phospha-2-thio-1,3-dioxan-2-yl） ethylene diamine （DPTDEDA, C12H26N2O4P2S2） was synthesized by the reaction of neopentyl glycol, phosphorus thio-chloride and 1,2-ethylenediamine, and characterized by elemental analysis, IR and ^1H NMR spectra. Its crystal structure was determined by single-crystal X-ray diffraction analysis and the thermal property was analyzed by TG analysis. The crystal structure belongs to monoclinic, space group P21/c, with a = 14.557（16）, b = 11.299（12）, c = 12.163（13）A,β = 98.707（19）^o, Dc = 1.305 g/cm^3, Z = 4, γ = 0.71073A,μ（MoKa） = 0.447 mm^-1, Mr = 388.41, V = 1977（4）A3, F（000） = 824, S = 1.107, the final R = 0.0478 and wR = 0.0810 for 1738 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the crystal structure is centrosymmetrically distributed through 1,2-ethylenediamine to join two distorted six-membered rings. The weak N-H…S interactions are observed and link the molecules into sheets. TG analysis shows that the title compound has good thermal stability and char-forming capability, which are required for an excellent intumescent fire retardant.
基金support for these studies from Gdańsk University of Technology by the DEC-8/2020/IDUB/I.3.3 grant under the Argentum-‘Excellence Initiative-Research University’program is gratefully acknowledged.Ł.P。
文摘The phospha-Wittig(phosphanylphosphinidene titanium(IV)complex)and phospha-Peterson(lithiated diphosphane)reactions were used to obtain phosphanylphosphaalkenes with the general formula XYCvP-PtBu_(2)(X=alkyl or aryl group or H;Y=alkyl or aryl group).Therefore,two series of reactions with different ketones and aldehydes were performed.Examination revealed that the two methods are complementary.For smaller carbonyl compounds,the phospha-Wittig reaction was shown to be a much better method,while for larger substituents(mainly aromatic),the phospha-Peterson reaction was shown to be a reliable method.These studies led to,among other things,the isolation of seven phosphanylphosphaalkenes in crystalline form after the phospha-Peterson reaction:(Ph)_(2)CvP-PtBu_(2)(3a),Z-(Ph)(4-CN-Ph)CvP-PtBu_(2)(3c),(4-CN-Ph)_(2)CvP-PtBu_(2)(3d),(4-MeO-Ph)_(2)CvP-PtBu_(2)(3e),E-tBu(Ph)CvP-PtBu_(2)(3f),E-{(Me)_(2)N-Ph}(H)CvP-PtBu_(2)(4d)and E-PhPh(H)CvP-PtBu_(2)(4e).The corresponding compounds were obtained in high yields under mild conditions,and more importantly,these new species are relatively air-and absolutely moisture-stable,especially those originating from aldehydes.In addition,a comprehensive DFT study helped us to establish not only the key factors crucial for effective phospha-Wittig-based synthesis of CvP-P species but also the consecutive steps along the reaction path leading to the formation of these compounds.
