N-(5,5-二甲基-1,3,2-二氧杂己内磷酰基)取代苯甲醛腙的合成及其阻燃性能

环状磷酸酯;水合肼;膨胀型阻燃剂;N-(5;5-二甲基-1;3;2-二氧杂己内磷酰基)取代苯甲醛腙的合成及其阻燃性能     

Synthesis,Crystal Structure and Flame Retardance of 2-(3-Silatranylpropylamino)-4-phenyl-5,5-dimethyl-1,3,2-dioxaphosphorinane-2-oxide

The title compound, 2-(3-silatranylpropylamino)-4-dichlorophenyl-5,5-dimethyl-1,3,2-dioxaphosphorinane-2-oxide(2(C_(20)H_(33)N_2O_6Psi)·C_2H_6O·CH_4O, Mr = 991.20), has been synthesized by the nucleophilic substitution reaction of 2-chloro-4-phenyl-5,5-dimethyl-1,3,2-dioxaphosphorinane-2-oxide with γ-aminopropylsilatrane, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 10.3783(15), b = 11.2402(17), c = 12.1675(18) ?, a = 70.653(4), b = 82.908(4), g = 85.690(4)°, V = 1328.1(3) ?3, Z = 1, Dc = 1.239 g/cm~3, μ = 0.19 mm~(-1), F(000) = 532, the final R = 0.0640 and wR = 0.2090 for 3615 observed reflections with I 2s(I). The cyclic dioxaphosphorinane ring in the molecule adopts a thermodynamically stable cis conformation, while the silatrane fragment forms a cage-like structure in which there exists an intramolecular Si?N donor-acceptor bond. In the crystal structure, centrosymmetrically related molecules are linked by pairs of N–H···O hydrogen bonds into dimers, generating rings with graph-set motif R22(8). Furthermore, a couple of O(7)–H(10)···O(3) hydrogen bonds were formed by O atom of P=O and H atom from hydroxyl in the solvent ethanol. Thermal property of the compound was also studied by means of thermogravimetry(TGA). The thermal analysis and preliminary fireproofing test show that the title compound has good flame retardance.     

Crystal Structure of cis-2-[(P, P-Diethoxy)phosphono(m-nitro)benzyloxy]-4-Phenyl-5,5-Dimethyl-1,3,2-Dioxaphosphorinane 2-Sulfide

The crystal structure of the title compound cis-2-[(P, P-Diethoxy)phosphono(m-nitro)benzyloxy]-4-Phenyl-5,5-Dimethyl-1,3,2-Dioxaphosphorinane 2-Sulfide, C22H29NO8P2S, was determined by single crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P21/c, with Mr=529.49, a=9.888(2), b=20.831(4), c=12.797(3) , β=94.42(3)°, V=2628(1) 3, Z=4, Dx=1.338 g/cm3, λ=0.71073, μ=0.2796 mm-1 and F(000)=556. The structure was solved by direct methods. The final R factor is 0.052 and Rw is 0.057 for 1793 unique observed reflections [I≥3σ(I)]. A cis-configuration and a preferred chair conformation for the molecule have been established by X-ray diffraction analysis. The results presented also give a good explanation to the correlation between the configurational assignments and the regularity in the chemical shifts of C4-H and 31P NMR.     

Synthesis and Crystal Structure of 5,5-Dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexene-1-one

The title compound 5,5-dimethyl-2-(4-chlorophenyl)(3-hydroxy-5,5-dimethyl-2-cyclohexen-1-one-2-yl)methyl-3-(4-methoxyphenylamino)-2-cyclohexen-1-one has been synthesized,and its crystal structure was characterized by X-ray single-crystal diffraction. The crystal belongs to monoclinic,space group P21/c with a=9.4193(13),b=26.915(4),c=21.188(3),β =101.906(3)°,V =5256.2(13)3,Z =4,C60H68Cl2N2O8,Mr=1016.06,Dc=1.284 g/cm3,F(000)=2160,λ(MoKα)=0.71073,μ=0.182 mm–1,R=0.0530 and wR=0.1131 for 4128 observed reflections (I>2σ(I)). X-ray analysis reveals that there are two independent molecules in the unit and the cyclohexenone rings adopt different conformations. In addition,there are four intramolecular hydrogen bonds in the title molecule.     

Synthesis and Crystal Structure of Cis 2-（6-Chloro-3-pyridylmethylamino）-4-chlorophenyl- 5,5-dimethyl- 1,3,2-dioxaphosphinane 2-Oxides

1 INTRODUCTION Neonicotinioid insecticides as nicotinic acetyl-choline receptor inhibitors have attracted increasingattention because of its safety, low toxicity, wide andhigh activities[1, . A lot of new insecticides such as 2]imidacloprid, acetamiprd and nitenpyram have beencommercialized. It is found that most biologicallyactive nicotinic compounds contain 3-aminomethyl-pyridine moiety[3]. Due to their wide biological acti-vities, organic phosphorus heterocyclic compoundsplay an import…     

3,3-二甲基-9-(5,5-二甲基-3-羟基-2-环己烯-1-酮-2-基)-1-氧代-2,3,4,9-四氢化氧杂蒽的合成和晶体结构

标题化合物C23H26O4是由水杨醛与5，5-二甲基-1，3-环己二酮在N，N-二甲基甲酰胺中反应而得．结构通过单晶X-射线行射法确定，其晶体属于单料晶系，空间群P21/c，a=7．056（7），b=20.263（3），c=13．665（2）A，β＝93．32（1）°，V=1950．7（4）A3，Mr=366．46，Dc=1.248g／cm3，Z=4，μ（MoKa）=0．84cm－1，F（000）=784。晶体结构用直接法解出，经全矩阵最小二乘法对原子参数进行修正，最后的偏离因子R=0．068，Rw=0．075。晶体结构分析结果表明，分子中存在一个共轭的烯醇式结构。     

Synthesis and Crystal Structure of α-(3-Phenylureido)-α-(2,4-Dichlorophenyl) Methyl Phenylphosphinic Acid

1INThODUCT1ONInaprevi0uspaPer"',wereP0rtedthesyntheses0fsome1,3,4-diazaphospho-lidin-2-thione-4-oxidesandtheirhighselectiveherbicidalactivity.Althoughtherewereseveralreportsaboutthedesulphurisationofsomestraightchainthioureaderiva-tivest2'31,uptonow,thedesulphurisationreactionofcyclicthioureaderivativesutiliz-ingAgNO,-H,Osystemhasnotbeenstudied.InthispaPer,thedesulphurisation0fcis-3,4-diphenyl-5-(2,4-dichlorophenyl)-1,3,4-diazaphOSpholidin-2-thione-4-oasthecyclicsubstrateisrep0rtedfort…     

1,3-二联苯基-2，4-二吡啶基环丁烷的结构与光化学性质

通过反-1-(4-联苯基)-2-(4-吡啶基)乙烯(EI)在稀硫酸中的光二聚反应合成了r-1,c-2,t-3,t-4-1,3-双(4-联苯基)-2,4-二(4-吡啶基)环丁烷(II).用X射线衍射法测定了其结构.晶体II为单斜晶系,空间群为P2     

One-pot Synthesis and Crystal Structure of （1S,2R,3S,4R,5S）-1-Phenyl-2,4-dibenzoyl-3,5-difurylhexanol

(1S,2R,3S,4R,5S)-1-Phenyl-2,4-dibenzoyl-3,5-difurylhexanol 1 was synthesized by one-pot reaction of hypnone and furfurol in alkali H2O/EtOH solution and structurally defined to contain a chair-formed aliphatic carbocycle, on which the bulky substituents occupy the equatorial positions.     

Stereoselective Synthesis of 2-Chloro-4-Substituted-phenyl-5,5-Dimethyl-1,3,2-Dioxaphosphorinan-2-(Thi)ones

1,3,2-DioxaPhoSPhorinaneringsystemhasbeenasubjectofconsiderableinterestformanyyearsbecauseofitSdiversebiologicalachvitieSIl'21andcomPlicatedstereocheAnstryl"'].AsacontinuationofourinterestinthesynthesisandstereochendstryoncycliCPhosPhoruscomPoundsl"'l,wewouldlilietorePOrthereinthestereoselechvesynthesisof2-chloro-4-subshtUted-phenyl-5,5-ddriethyl-l,3,2-dioxaPhoSPhorinan-2-(thi)ones,whicharethekeyintermediatesforthesynthesesofl,3,2-dioxaPhoSPhohaanederivatives.Generallyspeaking,2-chloro…     

2,4,8,10-四氧杂-3,9-二磷杂螺环[5.5]十一烷-3,9-二氧-3,9-二取代苯甲醛腙的合成及其阻燃性能

以季戊四醇、三氯氧磷为原料合成了富含酸源(磷)、碳源的氯化螺环磷酸酯(SPDPC),再将其与水合肼、取代苯甲醛反应,合成了系列化合物2,4,8,10-四氧杂-3,9-二磷杂螺环[5.5]十一烷-3,9-二氧-3,9-二取代苯甲醛腙,利用元素分析、FTIR、1H NMR和MS测试技术对其结构进行了表征。目标化合物分子结构对称性高、分子量较大、含较多芳构型碳和磷杂环碳,热重(TG)和差热(DSC)分析结果表明,具有较高的热稳定性。将这些化合物添加于环氧树脂(E-44)中进行水平燃烧实验,当添加质量分数为10%时,样条燃烧长度在10~20 mm之间,均具有很好的自熄效果;同时,LO I达到28.7%左右,有较好的阻燃性能。     

Synthesis and Crystal Structure of 3,6-Dimethyl- 9-（4-b rom o p h enyl）- 1,8-oxo-2,7,10-trioxanth ene

The crystal structure of the title compound (C19H13BrO5) has been determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/c,with a=10.508(4),b=11.354(4),c=14.522(5),β=106.255(4)°,V=1663.4(10)3,Mr=401.20,Z=4,Dc=1.602 g/cm3,λ=0.71073,F(000)=808,μ= 2.498 mm-1,R=0.0337 and wR=0.0837 for 2200 observed reflections (I>2σ(I)). X-ray analysis reveals that the dihedral angles between planes 1 and 2,1 and 3,1 and 4,2 and 3,2 and 4,and 3 and 4 are 78.6,82.5,87.4,5.6,9.5 and 4.9°,respectively. There exists a conjugated system in the molecular structure.     

Synthesis,Crystal Structure and Theoretically Study of 2-(Dimethylamino)-1,3-dithiocyanatopropane and Its Isomer

2-(Dimethylamino)-1,3-dithiocyanatopropane(1) has been prepared as a key intermediate synthesizing a natural insecticide Cartap by the reaction of 1-dimethylamino-2,3-dichloropropane with sodium thiocyanate. The crystal structures of compound 1 and its isomer 1-(dimethylamino)-2,3-dithiocyanotopropane(2) formed during the reaction were determined by X-ray single-crystal diffraction. Bond lengths in both the compounds are common and fall within normal ranges. There are some weak C―H×××N hydrogen bonds in the lattice of compound 1, which makes it form a three-dimensional network, which stabilize the crystal structure. No classic hydrogen bonds were founded in its isomer(2), only van der Waals forces contribute to the stability of the structure. In addition, DFT and MP2 calculations with 6-311+G(d, p) basis set have also been carried out to investigate the thermodynamic properties of compounds 1 and 2. The research will be applied to the further investigation of the tautomerization of compounds 1 and 2.     

Crystal Structure of 2－Thio－2－（3＇－methyl－4＇－chloro－oxyphenyl）－1，3，2－benzodioxaphosphole

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ２－Ｔｈｉｏ－２－（３＇－ｍｅｔｈｙｌ－４＇－ｃｈｌｏｒｏ－ｏｘｙｐｈｅｎｙｌ）－１，３，２－ｂｅｎｚｏｄｉｏｘａｐｈｏｓｐｈｏｌｅＳｕｎＭｉｎｇ；ＬｉｕＸｉａｏ－Ｌａｎ；ＭｉａｏＦａｎｇ－Ｍｉｎｇ（Ｉｎｓｔｉｉｔ...     

Synthesis, Crystal Structure and Thermal Property of a Manganese(II) 4-Carboxyphenoxyacetate Complex

1 INTRODUCTION Organic aromatic carboxylic acids which com-monly possess multiple coordination modes are ex-cellent candidates for constructing supramolecularmetal complexes[1～6]. 4-Carboxyphenoxyacetic acid(4-CPOAH2), widely used in biological activitystudies, is a multidentate flexible ligand that not onlyhas versatile binding possibilities but also can formregular hydrogen bonds as both hydrogen-bond donorand acceptor. However, there have been few reportson the coordination chemistr…     

Synthesis and Crystal Structure of 2-tert-Butyl-5-（4-tert-butylbenzylthio）- 4-chloropyridazin-3 （2H） -one

IntroductionPyridazinone compounds show widespread biologi-cal activities[1—3], many of them have been developedand used as fungicides and acaricides[4,5]. Pyridaben isa novel pyridazinone derivative that shows acaricide andinsecticide properties and was…     

1,2,3-三(5,5-二甲基-1,3-二氧杂环己内磷酰氧基)苯的合成、 晶体结构及阻燃性能研究

以新戊二醇、三氯氧磷以及1,2,3-三羟基苯等为原料, 经过两步反应合成新型阻燃剂1,2,3-三(5,5-二甲基-1,3-二氧杂己内磷酰氧基)苯, 采用元素分析、FTIR、MS、1H NMR及X射线四圆衍射等技术确定了标题化合物的分子结构. 结构分析表明, 该标题化合物属于三斜晶系, P-1空间群, 每个结构单元含有2个分子, 晶胞参数为a＝0.70450(14) nm, b＝1.2850(3) nm, c＝1.5609(3) nm, α＝69.19(3)°, β＝86.29(3)°, γ＝86.60(3)°, V＝1.3171(5) nm3, Dc＝1.438 g/cm3, μ＝0.286 mm－1, F(000)＝600, Z＝2, 由4635个独立衍射点得到最终偏离因子[I＞2σ(I)] R＝0.0574, Rw＝0.1061. 实验分析表明, 该标题化合物具有良好的热稳定性和成炭性, 对环氧树脂具有较好的阻燃效果, 最佳添加量为20%.     

Synthesis and Biological Activity of Cis 2-(6-Chloropyridine-3-yl)methylamino-4-substitutedphenyl-5,5-dimethyl-1,3,2-dioxaphosphinane 2-Oxides

A series of novel, asymmetric-cyclic phosphoramides containing substituted pyridine were synthesized via the condensation reactions of trans 2-chloro-4-substitutedphenyl-5, 5-dimethyl-1,3,2-dioxaphosphinane 2-oxide with 2-chloro-5-aminomethylpyridine or 3-aminomethylpyridine. The reactions show good stereoselectivity. Only the cis isomer from configuration inversion was obtained, which is the thermodynamic stable product. The structures of the products were characterized by ¹H NMR, ³¹P NMR, IR, MS, and elemental analysis. The configuration of the product was determined by X-ray diffraction analysis. The results of preliminary bioassay showed that the new compounds possess potential insecticidal and fungicidal activities.     

1-苯基-5-(3,4-二甲氧基苯基)-3-羟基吡唑的合成和晶体结构

标题化合物(I)是由 1-苯基-5-(3, 4-二甲氧基苯基)-3-吡唑烷酮在 FeCl3催化下被氧气氧化得到的。它的结构经过了元素分析、IR、1H NMR 的表征,用 X-射线衍射法测定了化合物的晶体结构。C17H16N2O3(I)的晶体学参数分别为:三斜晶系,P1空间群,a = 6.6600(13),b = 8.4200(17),c = 14.060(3) ?,α= 85.61(3), β= 76.89(3), γ= 81.18(3)?, Z = 2, Dc= 1.298g/cm3, V = 758.1(3) ?3, Mr = 296.32,μ= 0.090 mm–1, F(000) = 312, R = 0.048,wR = 0.1231。结构测定表明化合物的吡唑环存在着一个大的共轭体系,含有一个稳定的烯醇结构,分子通过分子间的氢键形成了网状的结构。     

Synthesis and Crystal Structure of Rubidium Lanthanum Tetraacetate,RbLa(CH3COO)4

The anhydrous rubidium tetraacetato lanthanate, RbLa(CH₃COO)₄, is obtained together with Rb₂La(CH₃COO)₅(H₂O) as colourless single crystals from a 1 : 2 mixture of Rb₂CO₃ and La(CH₃COO) · 1.5 H₂O in acetic acid by slow evaporation. The crystal structure [orthorhombic, Pnnm, Z = 2, a = 1242.0(3), b = 1650.1(4), c = 698.0(4) pm, R = 0.028, R_w = 0.071] contains La³⁺ nine coordinate by oxygen atoms of six acetate ligands. The polyhedra are connected to dimers and further to double chains running parallel to [001]. These [La(CH₃COO)₄]^– double chains are surrounded by four like double chains and connected by Rb⁺ ions that are seven coordinate by oxygen atoms.