Preparation and some reactions of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5] undecane-3,9-disulfide

3, 9-Dichloro-2, 4, 8, 10-tetraoxa-3, 9-diphosphaspiro[5. 5]undecane-3,9-disulfide (I), has been synthesized by treating a dimethylacetamide solution of 2, 4, 8, 10-tetraoxa-3,9-diphosphaspiro[5. 5]undecane-3, 9-disulfide (III) with carbon tetrachloride. A number of other known methods for converting dialkyl phosphorothioites to thiophosphorochloridates were also applied to III, but all failed to produce I. Chlorination of either I or III gave an acyclic product, 4, 4-bis(chloromethyl)-1, 1, 7, 7-tetrachloro-2, 6-dioxa-1, 7-di-phosphaheptane-1, 7-dioxide (IV), in nearly quantitative yield. The same compound was also obtained by the previously known method of chlorinating 3, 9-dichloro-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5.5]undecane (II). The treatment of pentaerythritol with phosphorus pentachloride gave IV in minor amount along with a 25% yield of 4,4-bis-(chloromethyl)-1-chloro-2, 6-dioxa-1-phosphacyclohexane-1-oxide (VII). The hydrolysis of I in heated aqueous sodium carbonate gave, after acidification, 3,9-dihydroxy-2,4,8,10-tetraoxa-3, 9-diphosphaspiro[5. 5]undecane-3, 9-disulfide (VIII). A number of derivatives were prepared by reaction of I with phenoxides and amines. The corresponding thio-phosphorofluoridate XI was prepared by treatment of I with potassium fluoride in dioxane.     

Chiral Separation of Spiro-compounds and Determination Configuration

Chiral spirocyclic compounds have attracted the attention of scholars and scientists owing to their potential applications in the pharmaceutical industry as either active pharmaceutical ingredients, catalysts in synthesizing active enantiomers, or as surface modifiers on silica particles to resolve entantiomers. In this study, five spiro compounds of 3,9-diphenyl-2,4,8,10-tetraoxaspiro[5.5]-undecane（1）, 3,9-（4-methoxyphenyl）-2,4,8,10-tetraoxaspiro [5.5] -undecane（2）, 3,9-（4-methylphenyl）-2,4,8,10-tetraoxaspiro [5.5] -undecane（3）, 4,4＇-（2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyl）dibenzoic acid（4） and 3,9-di（4-formyl-phenyl）-2,4,8,10-tetraoxa-spiro[5.5]-undecane（5） were synthesized by grinding pentaerythritol with benzaldehyde, 4-methoxybenzaldehyde, 4-methylbenzaldehyde, 4-carboxybenzaldehyde or terephthalaldehyde monoacetal in the presence of InI3r3 under solvent-free conditions. A normal phase HPLC method was successfully developed to resolve entantiomers of compounds 1--5 on a chiral column. Specific optical rotation of R or S entantiomers（1） was determined and the corresponding configurations were proposed based on Lowe＇s rule.     

含硫环状膦酸酯衍生物的合成及其热性能

以三氯化磷、苯和硫粉为原料,用离子液体法绿色合成了硫代苯基膦酰二氯(3);3与季戊四醇或新戊二醇反应合成了两种新型含硫磷系阻燃剂--2,4,8,10-四氧杂-3,9-二磷杂螺环[5.5]十一烷-3,9-二硫-3,9-二苯(1)或5,5-二甲基-2-苯基-2-硫代-1,3-二氧-2-磷杂环己烷(2).用~1H NMR,IR,DSC和TG对其结构和性能进行了表征.结果表明,1具有良好的成炭性和热稳定性.     

阻燃中间体3,9-二氯-2,4,8,10-四氧代-3,9-二磷杂螺[5.5]十一烷的合成

以PCl3和季戊四醇为原料合成了中间体3,9$C二氯-2,4,8,10$C四氧代-3,9-二磷杂螺[5.5]十一烷,产率达99.6%.对反应条件进行了优化,最佳反应条件为:PCl3和季戊四醇摩尔比为2.5∶1,反应温度80℃,反应时间1.5h.     

聚缩醛螺胞二醚的合成及结构表征

在I₂催化剂的作用下, 利用苯甲醛与季戊四醇反应, 制备了聚缩醛螺胞二醚的模型化合物3,9-二苯基-2,4,8,10-四氧杂螺[5.5]十一烷(1). 在此基础上, 利用1,3-苯二甲醛与不同摩尔比的季戊四醇合成了化合物1,3-二(2,6-二氧杂-4,4-二羟甲基环己基)苯(2)和2,4,8,10-四氧杂-3,9-二(3'-甲酰基苯基)螺[5.5]十一烷(3). 化合物2与化合物3反应, 制成标题化合物聚缩醛螺胞二醚4, 收率为95.4%. 用FTIR, ¹H NMR对化合物1～4的结构进行了表征. 发现在含有手性轴化合物1, 3, 4的¹H NMR谱中, 4个亚甲基中的8个氢原子裂分为4组双峰, 而不含有手性轴化合物中的4个亚甲基中的8个氢原子不裂分, 是个单峰. 这种不同不是由于化合物中刚性环所致, 而是由于有无手性轴造成的.     

REACTION OF PENTAERYTHRITOL WITH DIETHYL PHOSPHOROCHLORIDATE PENTAERYTHRITOL BIS-, TRIS- AND TETRAKIS(DIHYDROGEN PHOSPHATES)

Abstract

Reaction of pentaerythritol 1 with 1, 2 or 3 equivalents of diethyl phosphorochloridate 2 yielded pentaerythritol tris(diethyl phosphate) 5. Treatment of pentaerythritol with 4 or more equivalents of 2 gave pentaerythritol tetrakis(diethyl phosphate) 6. Transesterification of 5 and 6 with trimethylsilyl chloride and sodium iodide in acetonitrile followed by treatment with water gave pentaerythritol tris (dihydrogen phosphate) 7 and pentaerythritol tetrakis(dihydrogen phosphate) 8 respectively. Pentaerythritol bis(dihydrogen phosphate) 9 was prepared by the hydrolysis of 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro [5,5] undecane 3,9-dioxide 10. The compounds 7,8 and 9 were isolated as anilinium salts and characterized by 1H, 13C and 31P NMR spectra.     

Synthesis and thermal properties of spiro phosphorus compounds

Intumescent materials, 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5,5]-undecane-3,9-dioxide and 3,9-dichloro-2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5,5]-undecane having the capacity to produce dehydrating agent, blowing agent, and undergo carbonization during burning have been synthesized. The thermal behavior of the synthesized materials was investigated using differential thermal analysis, thermal volatilization analysis, programmed vacuum pyrolysis–mass spectrometry, flash pyrolysis–mass spectrometry and off-line pyrolysis–gas chromatography–mass spectrometry. The materials show exothermic degradation after 250 °C. Monitoring the release of hydrogen chloride and water, the blowing agents for the production of carbon foam, clearly indicated the superior performance of the pentavalent phosphorus compound over the trivalent phosphorus compound. The major gaseous degradation products released during pyrolysis showed the presence of sufficient quantities of several alkyl-substituted benzenes and fused aromatics. Suitable degradation mechanism has been proposed and discussed to explain the formation of various organics during thermal degradation.     

Synthesis and structure of 2,5,7,10-tetramethyl-2,4,8,10-tetraazabicyclo[4.4.0]decane-3,9-dione

2,5,7,10-Tetramethyl-2,4,8,10-tetraazabicyclo[4.4.0]decane-3,9-dione, a regioisomer of the previously known 2,5,7,8-tetramethyl-2,4,8,10-tetraazabicyclo[4.4.0]decane-3,9-dione, has been synthesized, and its structure has been established by X-ray diffraction analysis. The bicyclic system of this molecule is formed by two heterocyclescis-annelated through the C(1)-C(6) bond. The relative configurations of the asymmetric centers areS for C(5), andR for C(7). In the monohydrate crystal studied, the molecules are linked by O...H-O_w and O...H-N type H-bonds forming a three-dimensional framework.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 136–138, January, 1995.     

Several transformations of 3-benzyl-9-carbethoxymethyl-3,9-diazabicyclo[3.3.1]nonane

The transformations of 3-benzyl-9-carbethoxymethyl-3,9-diazabicyclo[3.3.1]nonane (I) were studied. The dichloride of 9-(-chloroethyl)-3,9-diazabicyclo[3.3.1]nonane, which is readily cyclized in the basic form to 3,9-diazatricyclo[3.3.1.2^3,9]undecane (V), was synthesized by reduction of I with LiAlH₄ and debenzylation with subsequent replacement of the hydroxy group, in the alcohol formed, by chlorine. An unusual cleavage of the carboxymethyl residue to form the nitrogen-unsubstituted dichloride of 3,9-diazabicyclo[3.3.1]nonane (XI) occurs on treatment with thionyl chloride of the acid obtained by saponification and debenzylation of I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1372–1375, October, 1970.     

Structural basis for intumescence – study of model compounds containing spiro phosphorus moiety and polymers containing such units

Spiro phosphorus compounds play a vital role, in recent years, in imparting flame retardancy and intumescence to the polymers. To ascertain the mechanism of the intumescency, model spiro phosphorus compounds, i.e., 3,9-disubstituted-2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5.5]-undecan- 3,9-dioxide, were chosen (compound I : substitution is chloro group and compound II : substitution is hydroxo group). The model compounds were investigated using Differential Thermal Analysis (DTA) and Thermal Volatilization Analysis (TVA), Vacuum Pyrolysis-MS and Off-line Pyrolysis followed by degradation product analysis by GC-MS. Dichlorospiro compound (I) showed an eruptive release of gases at 320°C and dihydroxo spiro compound (II) at about 350°C. The major components of the gas released were found to be HCl and H₂O in the case of compound I and H₂O in the case of compound II. The degradation product analysis showed the formation of wide varieties of substituted and condensed aromatic compounds in measurable quantities. From the acquired data, it is confirmed that the intumescence takes place within a narrow range of temperature (10°) and in this temperature limit extensive dehydrohalogenation and dehydration are taking place. Highly thermally reactive unsaturated hydrocarbons are produced which mainly undergo polymerization to aromatic compounds and finally to char.     

螺环三代树形大分子化合物的合成

以对苯二甲醛单缩醛与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷(1), 经水解, 再与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 8-(4-氧代环己烷基)-1,4-二氧杂螺[4.5]癸烷经芳构化形成2,6,10-三-(4-氧代环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(4), 再与甲醛进行羟醛缩合, 制成了2,6,10-三-(4-羟基-3,3,5,5-四羟甲基环己烷基)-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(5), 将5与过量的3反应, 得到了目标树形大分子化合物2,6,10-三-{15-(3,11-二(-4-(3-((9-(4-二氰基乙烯基)苯基)2,4,8,10-四氧杂螺[5.5]十一烷基)))-7-羟基-二螺[5.1.5.3]十六烷基)}-1,2,3,4,5,6,7,8,9,10,11,12-十二氢苯并[l]菲(6), 收率为18.1%. 产品结构经IR, 1H NMR, MS和元素分析进行了表征. 对影响反应的因素进行讨论.     

Synthesis of Spiro Heterocyclic Ketene Aminals

A method is provided for the synthesis of the previously unknown spiro heterocyclic ketene aminals, 3,9-bis(substituted-methylene)-2,4,8,10-tetraazaspiro[5.5]undecane 3 in moderate to excellent yields by cyclocondensation reaction of ketene dithioacetals 1 with tetrakis(aminomethyl)methane 2.     

无溶剂法合成4,6,10,12,16,18,22,24-八羟基-2,8,14,20-四-{(联三-(3-苯基-2,4,8,10-四氧杂螺[5.5]十一烷基))-(4-(2-(4,6,10,12,16,18,22,24-八羟基)杯芳基)苯基)}杯芳烃螺环树形大分子化合物

以对苯二甲醛、丙二腈为原料, 合成对苯二甲醛单缩醛, 再与季戊四醇反应得到了2,4,8,10-四氧杂-2,9-二(4-二氰基乙烯基苯基)螺[5.5]十一烷, 经水解, 与丙二腈反应, 制备了中间体2,4,8,10-四氧杂-2-(4-二氰基乙烯基苯基)-9-(4-甲酰基苯基)螺[5.5]十一烷(3). 用乙酸酐保护的对苯二甲醛单缩醛与间苯二酚反应, 制备了杯芳烯中间体(6). 将化合物6与过量的化合物3反应, 得到中间体7, 经水解后与过量的化合物6反应, 得到了4,6,10,12,16,18,22,24-八羟基-2,8,14,20-四-{(联三-(3-苯基-2,4,8,10-四氧杂螺[5.5]十一烷基))-(4-(2-(4,6,10,12,16,18,22,24-八羟基)杯芳基)苯基)}杯芳烃螺环树形大分子化合物(9). 总收率为12.7%. 产物结构用IR, 1H NMR, 13C NMR, MS 和元素分析进行了表征, 对影响反应的因素进行了讨论.     

Reaction of methyl 1-bromocyclohexanecarboxylate with zinc and 3-aryl-2-cyanopropenoic acids amides

Methyl 1-bromocyclohexanecarboxylate reacts with zinc and amides or methylamides of 3-aryl-2-cyanopropenoic acids to give 5-aryl-1,3-dioxo-2-azaspiro[5.5]undecane-4-carbonitriles or 5-aryl-2-methyl-1,3-dioxo-2-azaspiro[5.5]undecane-4-carbonitriles.     

Mass-spectrometric study of 3,9-diazabicyclo- and 3,9-oxaazabicylo[3.3.1]nonanes

The mass spectra of substituted 3,9-diazabicyclo- and 3,9-oxaazabicyclo[3.3.1]-nonanes were studied as a function of competitive distribution of the charge between the N₃ and N₉ and O₃ and N₉ atoms and the properties of the substituents attached to the heteroatoms. It is shown that a characteristic peculiarity of the fragmentation of 3,9-diazabicyclo[3.3.1]nonanes is fragmentation of the molecular ion with an open structure that is formed by cleavage of the C₁-C₂ bond. The formation of an amine fragment with retention of the bicyclic structure with an exocyclic double bond attached to the quaternary N₉ atom is characteristic for 3,9-oxaazabicyclo[3.3.1]nonanes. It is shown that this sort of behavior of the investigated compounds is determined by their structures and the properties of the heteroatoms in the saturated bicyclic systems.Communication 12 from the series Application of mass spectrometry in structural and stereochemical studies. See [1] for Communication 11.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 229–235, February, 1981.     

Reactions of Methyl Esters of 1-(α-Bromoisobutyryl)cyclohexanecarboxylic or 3-(1-Bromocyclohexyl)-2,2-dimethyl-3-oxopropanoic Acids with Zinc and Arylglyoxal

Methyl esters of 1-(-bromoisobutyryl)cyclohexanecarboxylic or 3-(1-bromocyclohexyl)-2,2-dimethyl-3-oxopropanoic acids react with zinc and arylglyoxals to form 3-aroyl-4,4-dimethyl-2-oxaspiro[5.5]undecane-1,5-diones or 1-aroyl-4,4-dimethyl-2-oxaspiro[5.5]undecane-3,5-diones, respectively. The former products react with phenylhydrazine, yielding 3-[aryl(2-phenylhydrazono)methyl]-4,4-dimethyl-2-oxaspiro[5.5]undecane-1,5-diones.     

Chemistry of bicyclic ureas 6. Synthesis of 2,4,8,10-tetraazabicyclo [4.4.0]-3,9-decanediones

Conclusions A method was developed for obtaining 2,4,8,10-tetraazabicyclo[4.4.0]-3,9-decanediones, which contain aromatic, alkaryl, and heteroaromatic substituents in the 7 position, by the condensation of 6-ureidohexahydro-2-pyrimidinones with the appropriate aldehydes in the presence of cationite KU-2 in the acid form.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1597–1601, July, 1980.     

Synthesis of substituted methyl 5,5-polymethylene-2,4-dioxotetrahydropyran-3-carboxylates

Dimethyl 2-(1-bromocyclohexylcarbonyl)-, 2-(1-bromocyclopentylcarbonyl)-, and 2-(1-bromocyclobutylcarbonyl)-2-methylmalonates reacted with zinc and aromatic aldehydes to give the corresponding methyl 1-aryl-4-methyl-3,5-dioxo-2-oxaspiro[5.5]undecane-4-, 6-aryl-9-methyl-8,10-dioxo-7-oxaspiro[4.5]-decane-9-, and 5-aryl-8-methyl-7,9-dioxo-6-oxaspiro[3.5]nonane-8-carboxylates.     

α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5] 十一烷基]}苯基卟啉星形化合物的合成

以对苯二甲醛、丙二腈、季戊四醇和吡咯为原料, 合成了含有螺环结构单元的中间体3-[4-(2,2-二氰基)乙烯基]苯基-9-(4-甲酰基)苯基-2,4,8,10-四氧杂螺[5.5]十一烷(3)和α,β,γ,δ-四-(4-甲酰基苯基)卟啉(4). 4与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[2-(5,5-二羟甲基-1,3-二噁烷基)]}苯基卟啉(5), 5与3的反应产物经10% NaOH 处理后, 再与过量的季戊四醇反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二羟甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(6), 6与乙酐、丙酐、苯甲酰氯反应, 得到α,β,γ,δ-四-{4-[3-(9-(4-(3- (9-(4-(2-(5,5-二乙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(7), α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二丙酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(8)和α,β,γ,δ-四-{4-[3-(9-(4-(3-(9-(4-(2-(5,5-二苯甲酰氧基甲基-1,3-二噁烷基))))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基)))苯基-2,4,8,10-四氧杂螺[5.5]十一烷基]}苯基卟啉(9)等三种卟啉星形化合物. 中间体1～6和星形化合物7～9均进行了IR, ¹H NMR, MS和元素分析等结构表征. 对影响反应的诸因素进行了讨论.      

A pentaerythritol‐derived spirodi­phospho­nate

The title spirodi­phospho­nate, 3,9‐di­methyl‐2,4,8,10‐tetraoxa‐3λ⁵,9λ⁵‐diphospha­spiro­[5.5]­un­decane‐3,9‐dione, C₇H₁₄O₆P₂, a polymer additive, has crystallographic symmetry 2. At 100 K, its six‐membered rings have chair conformations, with endocyclic torsion‐angle magnitudes in the range 51.87 (8)–58.93 (9)°. The P=O distance is 1.4749 (8) Å, while the P—C(methyl) distance is 1.7691 (12) Å.