SYNTHESIS OF N-ACYL, N-SULFONYL, AND "N-PHOSPHINYLPHOSPHA-LAMBDA-5-AZENES BY A REDOX-CONDENSATION REACTION USING AMIDES, TRIPHENYLPHOSPHINE, AND DIETHYL AZODICARBOXYLATE
SYNTHESIS OF N-ACYL, N-SULFONYL, AND "N-PHOSPHINYLPHOSPHA-LAMBDA-5-AZENES BY A REDOX-CONDENSATION REACTION USING AMIDES, TRIPHENYLPHOSPHINE, AND DIETHYL AZODICARBOXYLATE
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DOI：
10.1021/jo00210a027
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发表时间：
1985-01-01
影响因子：
3.6
通讯作者：
SMITH, CG
中科院分区：
文献类型：
--
作者：
BITTNER, S;ASSAF, Y;SMITH, CG
膦和酰胺与偶氮二甲酸二乙酯（DAD）反应生成磷-X5-氮烯。因此，当使用三苯基膦（TPP）时，芳香族酰胺和具有吸电子取代基的脂肪族酰胺得到N-酰基-P，P，P-三苯基磷杂-X_5-氮烯（5）。芳基磺酰胺和烷基磺酰胺均与TPP和DAD反应生成α-磺酰基磷杂-X5-氮烯（9）。二苯基膦酰胺（10）和氨基甲酸乙酯（12）也用TPP和DAD产生相应的磷腈（11和13）。仲羧酰胺和磺酰胺不与TPP和DAD反应。亚磷酸三乙酯与磺酰胺在DAD存在下的反应在类似的反应中产生亚磷酸酯（20），沿着相应的2 V，IV-二乙基磺酰胺和亚磷酸三乙酯与DAD的脱乙基加合物（23）。然而，亚磷酸三乙酯-DAD不能与羧酰胺得到亚磷酸酯，而是得到DAD和亚磷酸三乙酯的重排加合物（19）。三（二甲氨基）膦与磺酰胺和DAD反应，但产物是相应的IV-磺酰基氨基甲酸乙酯（26）而不是磷腈。三（二甲基氨基）膦与偶氮二甲酰胺（含有偶氮和甲酰胺基团的分子）反应，产生N，N-二甲基脲，同样没有形成磷腈。最后，三苯基胂与苯磺酰胺和DAD反应生成7-（苯磺酰基）三苯基胂-X_5-氮烯（30），而三苯基二苯乙烯与DAD和苯磺酰胺反应只生成三苯基氧化二苯乙烯。偶氮二甲酸二乙酯（DAD）-三苯基膦（TPP）氧化还原缩合体系的应用已被广泛接受。2，3通过还原剂（TPP）和氧化剂（DAD）的组合来消除水元素。在所有情况下，甜菜碱1是首先形成的中间体，并且当醇是反应物时，1与醇反应以通过五配位正膦的方式产生准硅鏻盐3。4-6然后进行SN 2反应，其中三苯基氧化膦（TPPO）是离去基团。方案Ⅰ显示了假定的机理，包括二烷氧基正膦（2），它已被证明是由甜菜碱1和2当量的醇ROH生成的。4，5 TPP被氧化成TPPO，而DAD被还原成肼二羧酸二乙酯（DH 2D）。“缩合”一词有些误导，因为氧化还原体系催化亲核取代，在这种情况下，亲核取代是带有酸性氢的中心被醇烷基化。该反应已被广泛使用，并已应用于各种酸性底物（例如羧酸、酚、羧酰亚胺、活性亚甲基化合物），p值约为11.7。由于羧酰胺的酸性不够，因此声称这种酰胺不可能通过该方法进行烷基化。然而，它是dem-
The reaction of phosphines and amides with diethyl azodicarboxylate (DAD) produced phospha-X5-azenes. Thus aromatic amides and those aliphatic amides with electron-withdrawing substituents gave JV-acyl-P, P, P-triphenylphospha-X5-azenes (5) when triphenylphosphine (TPP) was employed. Both aryl-and alkylsulfonamides reacted with TPP and DAD to produce the Ñ-sulfonylphospha-X5-azenes (9). Diphenylphosphinamide (10) and ethyl carbamate (12) also produced the respective phosphazenes (11 and 13) with TPP and DAD. Secondary carboxamides and sulfonamides did not react with TPP and DAD. The reaction of triethyl phosphite with sulfonamides in the presence of DAD produced the phosphorimidates (20) in an analogous reaction, along with the corresponding 2V, lV-diethylsulfonamides and the deethylated adduct of triethyl phosphite and DAD (23). Triethyl phosphite-DAD failed, however, to give a phosphorimidate with carboxamides but gave, instead, the rearranged adduct of DAD and triethyl phosphite (19). Tris (dimethylamino) phosphine reacted with sulfonamides and DAD but the products were the corresponding ethyl IV-sulfonylcarbamates (26) rather than the phosphazenes. Tris (dimethylamino) phosphine reacted with azodicarbonamide (a molecule which contains both the azo and carboxamide groups) with the production of lV, JV-dimethylurea, again without formation of the phosphazene. Finally, the reaction of triphenylarsine with benzenesulfonamideand DAD produced 7V-(phenylsulfonyl) tri-phenylarsa-X5-azene (30) but triphenylstibene with DAD and benzenesulfonamide only gave triphenylstibene oxide. Mechanistic possibilities for these reactions are also discussed.The use of the redox-condensation system diethyl azo-dicarboxylate (DAD)-triphenylphosphine (TPP) is well-established. 2, 3 Elimination of the elements of water is brought about by the combination of a reducing agent (TPP) and an oxidant (DAD). The betaine, 1, is the first formed intermediate in all cases and, when an alcohol is a reactant, 1 reacts with the alcohol to produce the qua-si-phosphonium salt, 3, by way of a pentacoordinate phosphorane. 4-6 An SN2 reaction, where triphenyl-phosphine oxide (TPPO) is the leaving group then follows. Scheme I shows what has been postulated as the mecha-nism5 and includesthe dialkoxyphosphorane (2) which has been shown to be produced from betaine 1 and 2 equiv of the alcohol, ROH. 4, 5 TPP is oxidized to TPPO while DAD is reduced to diethyl hydrazinedicarboxylate (DH2D). The term “condensation” is somewhat misleading as the redox system catalyzes nucleophilicsubstitution which is, in this case, the alkylation by alcohols of centers carrying an acidic hydrogen. This reaction has found general use and has been applied to various acidic substrates (eg, carboxylic acids, phenols, carboximides, activemethylene compounds) with p values to about 11.7 As carboxamides are not acidic enough, it was claimed7 that no alkylation of such amides is possible by this method. However, it was dem-