有机磷化合物的研究 ⅠⅣ.合成烷基膦酸单酯衍生物的新方法

Atherton与Todd等1945年就用亚磷酸二烷基酯在四氯化碳中与有机胺反应得到二烷基磷酰胺.我们曾成功地由二烷基亚磷(膦)酸在四氯化碳存在下与多种亲核试剂反应合成二烷基磷(膦)酸酯及其衍生物.实验表明二烷基亚膦酸的反应性和亚磷酸二烷基酯有很大差别,为进一步考察不同的三配位磷化合物在该反应中的反应性能,我们合成了己基亚膦酸单烷基酯并在四氯化碳中与各种亲核试剂进行氧化膦酰化反应,制得了相应的己基膦酸单酯衍生物,得率良好,为合成烷基膦酸单酯衍生物的新方法.     

N-糖基硫代亚脲基—(硫代)磷酰胺二芳基和二烷基酯的合成

二芳氧基磷酰肼(2a，2b)或二乙氧基硫代磷酰肼(4)与糖基异硫氰酸酯(5a-5b) 反应，生成相应的N-糖基硫代亚脲基—磷酰胺二芳基酯(6a-6d,7a-7d)和N-糖基硫 代亚脲基—硫代磷酰胺二乙基酯(8a-8d)．     

第五、六族元素的有机化合物在有机合成中应用的研究——Ⅱ.烷氧羰基亚甲基三苯基胂与脂族酮的反应及其自身的热裂

从β-羟基酸酯脱水制备α,β-不饱和酸酯的方法中经常伴有β,γ-不饱和酸酯的生成.与此相反,烷氧羰基亚甲基三苯基胂与脂族酮反应,生成纯的α,β-不饱和酸酯.后一反应的产物经核磁共振谱证明系顺、反异构体的混合物.甲氧羰基亚甲基三苯基胂经热裂可得反式丁烯二酸二甲酯和环丙烷1,2,3-三羧酸三甲酯.     

有机磷化合物的研究 ⅩⅩⅡ.亚甲基双(膦酸二烷基酯)及其衍生物

亚甲基双(膦酸二烷基酯)及其衍生物是一类能以通式1表示的化合物,其中1a、1b及1c、1d分别可视为丙二酸酯及乙酰乙酸酯的磷类似物,它们是重要有机合成试剂及金属配位体,但是这类化合物的研究与应用受到其合成方法的限制.本文报道基于甲基膦酸二乙酯(2)碳阴离子的磷(膦)酰化反应合成1的新方法.1的C-烷基化可得预期的3,后者也可由烷基膦酸二乙酯(4)的碳阴离子反应而得,或由二苯基膦酰氯经甲基化及相继的碳阴离子磷酰     

含磷拟除虫菊酯的研究III. 3-烷氧羰基-2, 2-二甲基环丙烷基 甲醛肟或甲基酮 肟和二烷氧基硫代磷酰氯的反应

本文研究了3-烷氧羰基-2,2-二甲基环丙烷基甲基酮肟或醛肟分别和二烷氧基硫代磷酰氯的反应,鉴定了它们的不同产物。结果表明,酮肟与磷酰氯缩合得硫代磷酸肟酯;醛肟与磷酰氯反应生成3-氰基环丙烷羧酸酯和相应的二烷基硫代磷酸,可能是经生成9再Beckmann裂解的机理。文中对上述结果进行了讨论。     

含磷拟除虫菊酯的研究III. 3-烷氧羰基-2, 2-二甲基环丙烷基 甲醛肟或甲基酮 肟和二烷氧基硫代磷酰氯的反应

本文研究了3-烷氧羰基-2,2-二甲基环丙烷基甲基酮肟或醛肟分别和二烷氧基硫代磷酰氯的反应,鉴定了它们的不同产物。结果表明,酮肟与磷酰氯缩合得硫代磷酸肟酯;醛肟与磷酰氯反应生成3-氰基环丙烷羧酸酯和相应的二烷基硫代磷酸,可能是经生成9再Beckmann裂解的机理。文中对上述结果进行了讨论。     

含磷拟除虫菊酯的研究 Ⅲ.3-烷氧羰基-2,2-二甲基环丙烷基甲醛肟或甲基酮肟和二烷氧基硫代磷酰氯的反应

本文研究了3-烷氧羰基-2,2-二甲基环丙烷基甲基酮肟或醛肟分别和二烷氧基硫代磷酰氯的反应,鉴定了它们的不同产物.结果表明,酮肟与磷酰氯缩合得硫代磷酸肟酯;醛肟与磷酰氯反应生成3-氰基环丙烷羧酸酯和相应的二烷基硫代磷酸,可能是经生成9再Beckmann裂解的机理.文中对上述结果进行了讨论.     

α-氨基烃基膦酸及其衍生物的合成与反应

本文报导合成α-氨基烃基膦酸(1)及其衍生物的新方法与反应。(一)提出用苯甲酰胺(或丙烯酰胺)和醛、亚磷酸三苯酯反应,经水解合成(1);(二)在BF_3·Et_2O催化下用磷酰胺或代磷酰胺、醛和亚磷酸三苯酯或苯基亚磷酸二苯酯反应,生成α-磷胺酰氨基(或硫代磷酰胺基)取代苄膦酸二苯酯或次膦酸苯酯(2)。经选择性脱去氨基保护基生成α-氨基膦酸二苯酯溴代盐(3);(三)二苯氧基氯磷、醛和磷酰胺(或硫代磷酰胺)在 ZnCl_2等路易斯酸存在     

脯氨酸催化的甲基酮与a-酮酸酯间的不对称Aldol反应

以脯氨酸为催化剂，实现了甲基酮与a-酮酸酯间的不对称Aldol反应，以43%-93%的产率和最高达81％的ee得到多种a-羟基酸酯。空间效应看来是影响反应活性和选择性的一个重要因素。丙酮表现出比丁酮高的反应活性，而在某些情况下 丁酮则呈现更高的对映选择性。     

有机磷化合物的研究 Ⅷ.酸性有机磷化合物的气相色谱

酸性磷(膦)酸酯与四甲基氢氧化铵的甲醇溶液反应制得的四甲基铵盐溶液,热解转化成O-甲基化产物用气相色谱鉴定。分离与鉴定了磷酸二烷基酯、磷酸单烷基酯、烷基膦酸单烷基酯和二烷基膦酸等,并讨论了烷基碳原子数和烷基的空间效应对校正保留时间(t′_R)及保留指数(I)的影响。     

Acetylene Phosphonates as Dienophiles: A Route to Carbocyclic and Aromatic Phosphonates and Diphos-Phonates

Abstract

Systematic research of unsaturated phosphonates, started at the end of the sixties, gave rise to a variety of acetylene phosphonic derivatives. The authors worked out two significant routes to these compounds, (1) action of PCl₅ upon some alkynes followed by HCl elimination which gives alkyne dichlorophosphonates. and (2) Arbuzov reaction of P_III esters with halo- and dihaloalkynes which gives different phosphono- and diphosphonoacetylenes. The phosphonic groups are electron-withdrawing, and acetylenephosphon-ates are typical dienophiles in Diels-Alder cycloaddition of diene-donor/dienophile-acceptor type. Phosphonic esters are less active than corresponding dichlorophosphonates, but diphosphonic esters expose high reactivity. Haloethyne- and dialkylaminoethynephosphonates are sufficiently active in the reaction with simple dienes (butadiene, iso-prene, 2,3-dimethylbutadiene and piperylene), but we were not able to introduce alkyl- or arylacetylene phosphonic esters in the cycloaddition.     

A novel and convenient method for synthesis of carbamoyl and thiocarbamoyl phosphonates

A simple, efficient, and general method has been developed for the synthesis of carbamoyl and thiocarbamoyl phosphonic esters using CaCl₂ as an efficient Lewis base catalyst. Carbamoyl and thiocarbamoyl phosphonic esters were obtained in good yield (37%–65%) and purity under mild conditions by the reaction of diethyl phosphite with isocyanates and isothiocyanates in the presence of CaCl₂. This method is easy, rapid, and good‐yielding reaction for the synthesis of carbamoyl and thiocarbamoyl phosphonic esters. © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:250–253, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20538     

Über eine Reaktion von o-Hydroxybenzylalkoholen mit Estern von Säuren des Phosphors mit der Koordinationszahl 3

Abstract

o-Hydroxybenzyl alcohol reacts with trimethyl phosphite under smooth conditions to o-hydroxyphenylmethane phosphonic acid dimethyl ester. This unusual reaction is of widest applicability. Derivatives of o-hydroxybenzyl alcohol independent of type, number or position of substituents in the ring, react with alkyl esters of phosphorous, phosphonous or phosphinous acids in an analogous process, forming the corresponding o-hydroxyphenylmethane phosphonic or phosphinic esters or phosphine oxides.     

New mixed phosphonate esters by transesterification of pinacol phosphonates and their use in aldehyde and ketone coupling reactions with nonstabilized phosphonates

Alkylpinacol phosphonates were prepared by rhodium-catalyzed olefin hydrophosphorylation, and attempted alpha-deprotonation of the pinacol derived alkyl phosphonates resulted in ring cleavage. The propensity of the alkylpinacol phosphonates to undergo ring opening was exploited to prepare phosphonic acid monomethyl esters in high yield by transesterification in acidulated methanol. Esterification and alkylation with aldehydes or ketones gave beta-hydroxy mixed phosphonate esters. tert-Butyl and benzylic phosphonate ester protective groups were introduced to improve the efficiency and functional group compatibility of beta-hydroxy phosphonate saponification. The beta-hydroxy phosphonic acid monomethyl esters were dehydrated with diisopropylcarbodiimide, which gave oxaphosphetane intermediates that collapse to an olefin. The overall reaction sequence complements the arsenal of Horner-Wadsworth-Emmons-type coupling reactions.     

Kinetics and mechanism of the hydrolysis of esters of hydroxymethylphosphonic and hydroxymethylethylphosphinic acids

Conclusions The reactivity of ethyl esters of phosphonic and phosphinic acids containing a hydroxymethyl group at the phosphorus atom in their reaction with hydroxide anion is usually high as a consequence of intramolecular catalysis of the cleavage of the ester bond involving the ionized OH group. The spontaneous hydrolysis of these esters proceeds according to a mechanism analogous to that for other alkyl esters of tetracoordinated phosphorus acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 9, pp. 2139–2140, September, 1985.     

Reaction Pathways upon Interaction of Allenic Phosphonates with Selenyl Chlorides

Abstract

Studies were performed on the reaction between alkyl- and arylselenyl chlorides with esters of allenic phosphonic acids, variously substituted at their terminal C-atom. With the esters of the C-3 diasubstituted acids the reaction is highly regioselective and only oxaphosphol heterocyclization occurs to 2,5-dihydro-1,2-oxaphosphols 21-e. With the esters of the propadiene phosphonic acid the reaction is regio- and (Z)-stereoselective: only the 2,3-adducts 3a-b are formed, where the (Z)-isomer and the allenic phosphonates 4a-b are prevalent, as a result of 1,3-sigmatropic isomerization of 3a-b. With the esters of the C-3 monosubstituted acids, complex reaction mixtures are formed. From them were isolated: (E)- and (Z)-isomers of 2,5-dihydro-1,2-oxaphosphols 2f-j; (E)-and (Z)-isomers of the 2,3-adducts 3c-h; (E)-and (Z)-isomers of 4c-f; and (E)-and (Z)-isomers of the 1,2-adducts 5a-d. The reaction partially loses its regioselectivity, but the (Z)-stereoselectivity is preserved:     

Selective Esterification of Phosphonic Acids

Here, we report straightforward and selective synthetic procedures for mono- and diesterification of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono- or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The substrate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small- and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30 °C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters. ³¹P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.     

Synthese von phenoxygruppenhaltigen Derivaten der Methandiphosphonsäure

Synthesis of Phenoxy Derivatives of Methanediphosphonic Acid Derivatives of the methanediphosphonic acid containing different numbers of phenoxy groups were prepared by Michaelis-Arbusov reaction of iodomethane phosphonic acid esters with phosphorous acid esters and by reaction of methane diphosphonic acid tetrachlorid with sodium phenolate. The obtained products were investigated by means of n.m.r. spectroscopy.     

Synthesis of o-Carboranyl Containing Esters of Pentavalent Phosphorus Acids

Abstract

A new method for the synthesis of o-carboranyl containing phosphoric, phosphonic and phosphinic acid esters, where the o-carboranil group is in the ester group, has been developed. The propargyl esters of these acids were prapared in two ways: by the reaction of phosphorus acid salts with propargyl chlorid and by interaction of propargyl alcohol with acid chlorides in the presence of Et₃N. The propargyl esters have been converted into carboranyl containing compounds upon treatment with decaborane and dimethyl aniline     

Reaction in the system trialkyl phosphite-carboxamide or secondary amine

Conclusions A study was made of reaction in the system: triethyl phosphite-amide (amine)-paraform(benzaldehyde). The reaction leads to the formation of the corresponding esters of aminomethyl(alkyl)phosphonic acids.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2773–2776, December, 1971.