- Reactions of Primary Amines and Alcohols with 4-Toluoyl Azide
-
Primary amines 2 react with 4-toluoyl azide 1 in non-nucleophilic solvents in a clear second order reaction, which is strongly dependent on the size of the amine 2 and the solvent polarity (k2: 15.51 (2a), 0.83 (2b) and 0.19 (2c) l/mol*min; ΔH(excit.) = 22.1 kJ/mol, ΔS(excit.) = -170.5 J/mol*K ).Drastic changes occur in the presence of nucleophilic solvents.With nucleophilic amines 2 added to these in the solutions a concurrent reaction with alcohols 4 yielding 4-toluoyl ester 5 is observed.This is especially dominating with the "smallest" alcohol methanol (4a) and/or effectively promoted by "bulky" amines (2b, 2c; up to 99percent 5a).Compared with the pure alcoholysis a huge acceleration of the ester formation, proportional to the concentration of the nucleophilic amine 2, is observed.The reaction mechanism is discussed with special emphasis on steric effects in the competition of nucleophiles for the aroyl azide 1. - Keywords.Aroyl azide; 4-Toluoyl azide; Alcoholysis; Aminolysis; "Nucleophilic catalysis"; Kinetics; Steric effects.
- Ulbricht, Mathias,Boehme, Peter,Hartmann, Udo
-
-
Read Online
- The electronic absorption spectra of some acyl azides. Molecular orbital treatment
-
The electronic absorption spectra of benzoyl azide and its derivatives: p-methyl, p-methoxy, p-chloro and p-nitrobenzoyl azide were investigated in different solvents. The observed spectra differ basically from the electronic spectra of aryl azides or alkyl azides. Four intense π-π* transitions were observed in the accessible UV region of the spectrum of each of the studied compounds. The contribution of charge transfer configurations to the observed transitions is rather weak. Shift of band maximum with solvent polarity is minute. On the other hand, band intensity is highly dependent on the solvent used. The observed transitions are delocalized rather than localized ones as in the case with aryl and alkyl azides. The attachment of the C{double bond, long}O group to the azide group in acyl azides has a significant effect on the electronic structure of the molecule. The arrangements as well as energies of the molecular orbitals are different in acyl azides from those in aryl azides. The first electronic transition in phenyl azide is at 276 nm, whereas that of bezoyle azide is at 251 nm. Ab initio molecular orbital calculations using both RHF/6-311G* and B3LYP/6-31+G* levels were carried out on the ground states of the studied compounds. The wave functions of the excited states were calculated using the CIS and the AM1-CI procedures.
- Abu-Eittah, Rafie H.,Mohamed, Adel A.,Farag,Al Omar, Ahmed M.
-
-
Read Online
- Synthesis of: N -methylated amines from acyl azides using methanol
-
The transformation of acyl azide derivatives into N-methylamines was developed using methanol as the C1 source via the one-pot Curtius rearrangement and borrowing hydrogen methodology. Following this protocol, various functionalised N-methylated amines were synthesized using the (NNN)Ru(ii) complex from carboxylic acids via an acyl azide intermediate. Several kinetic studies and DFT calculations were carried out to support the mechanism and also to determine the role of the Ru(ii) complex and base in this transformation.
- Chakrabarti, Kaushik,Dutta, Kuheli,Kundu, Sabuj
-
supporting information
p. 5891 - 5896
(2020/08/21)
-
- Deoxygenative Amination of Azine-N-oxides with Acyl Azides via [3 + 2] Cycloaddition
-
A transition-metal-free deoxygenative C-H amination reaction of azine-N-oxides with acyl azides is described. The initial formation of an isocyanate from the starting acyl azide via a Curtius rearrangement can trigger a [3 + 2] dipolar cycloaddition of polar N-oxide fragments to generate the aminated azine derivative. The applicability of this method is highlighted by the late-stage and sequential amination reactions of complex bioactive compounds, including quinidine and fasudil. Moreover, the direct transformation of aminated azines into various bioactive N-heterocycles illustrates the significance of this newly developed protocol.
- Ghosh, Prithwish,Han, Sang Hoon,Han, Sangil,Kim, Dongeun,Kim, In Su,Kim, Saegun,Kwon, Na Yeon,Mishra, Neeraj Kumar
-
p. 2476 - 2485
(2020/03/13)
-
- Direct conversion of carboxylic acids to various nitrogen-containing compounds in the one-pot exploiting curtius rearrangement
-
Herein we report, a single-pot multistep conversion of inactivated carboxylic acids to various N-containing compounds using a common synthetic methodology. The developed methodology rendered the use of carboxylic acids as a direct surrogate of primary amines, for the synthesis of primary ureas, secondary/tertiary ureas, O/S-carbamates, benzoyl ureas, amides, and N-formyls, exploiting the Curtius reaction. This approach has a potential to provide a diversified library of N-containing compounds, starting from a single carboxylic acid, based on the selection of the nucleophile.
- Kumar, Arun,Kumar, Naveen,Sharma, Ritika,Bhargava, Gaurav,Mahajan, Dinesh
-
p. 11323 - 11334
(2019/09/10)
-
- Visible Light-Induced Regioselective Cycloaddition of Benzoyl Azides and Alkenes to Yield Oxazolines
-
Visible light catalysis allows the regioselective synthesis of oxazolines in high yields. The mild photosensitized manifold leverages the intermolecular formation of oxazolines with a wide functional group tolerance on both benzoyl azides and alkenes part
- Bellotti, Peter,Brocus, Julien,El Orf, Fatima,Selkti, Mohamed,K?nig, Burkhard,Belmont, Philippe,Brachet, Etienne
-
supporting information
p. 6278 - 6285
(2019/05/24)
-
- Synthesis of Acyl Azides from 1,3-Diketones via Oxidative Cleavage of Two C-C Bonds
-
A metal-free PhI(OAc)2-mediated method for the synthesis of acyl azides through oxidative cleavage of 1,3-diketones is described. This method is shown to have a broad substrate scope, providing a useful tool for multiproduct synthesis in a single procedure. A possible reaction pathway is proposed based on mechanistic studies.
- Yu, Tian-Yang,Zheng, Zhao-Jing,Dang, Tong-Tong,Zhang, Fang-Xia,Wei, Hao
-
p. 10589 - 10594
(2018/09/06)
-
- Palladium-Catalyzed One-Pot Synthesis of N -Sulfonyl, N -Phosphoryl, and N -Acyl Guanidines
-
An efficient palladium-catalyzed cascade reaction of azides with isonitrile and amines is presented; it offers an alternative facile approach toward N -sulfonyl-, N -phosphoryl-, and N -acyl-functionalized guanidines in excellent yield. These series of substituted guanidines exhibit potential biological and pharmacological activities. In addition, the less reactive intermediate benzoyl carbodiimide could be isolated by silica gel column flash chromatography in moderate yield.
- Qiao, Guanyu,Zhang, Zhen,Huang, Baoliang,Zhu, Liu,Xiao, Fan,Zhang, Zhenhua
-
supporting information
p. 330 - 340
(2018/01/12)
-
- Iridium(III)-Catalyzed Selective and Mild C-H Amidation of Cyclic N-Sulfonyl Ketimines with Organic Azides
-
A general protocol for iridium catalyzed direct C?H amidation of cyclic N-sulfonyl ketimines using sulfonyl, acyl and aryl azides as nitrogen source is reported herein. The reaction takes place at room temperature with acyl and aryl azides, while an elevated temperature needed with sulfonyl azides to furnish aminated sultams in excellent yields with complete chemo and regioselectivity, thus providing a robust and environmentally benign process to the synthesis of aminosultams. (Figure presented.).
- Maraswami, Manikantha,Chen, Gang,Loh, Teck-Peng
-
supporting information
p. 416 - 421
(2017/11/13)
-
- An investigation on practical synthesis of carboxylic acid derivatives using p-toluenesulfonyl chloride
-
Carboxylic acid derivatives are well recognized as important class of reagents frequently used in the preparation of a variety of fine or special chemicals such as amides, esters, peptides, drugs, and dyes. Although several methods were developed for the preparation of these compounds, many of them present difficulties, including low yield, high reaction temperature, harsh reaction conditions, tedious work-up, and incompatibility with scale-up. Methods: The synthesis of carboxylic anhydrides is developed through the reaction of carboxylic acids with TsCl in the presence of K2CO3 and acetonitrile as a solvent under ultrasound irradiation and conventional conditions. In addition, one-pot synthesis of acyl azides was carried out in the presence of produced carboxylic anhydrides and the addition of sodium azide under identical condition. Results: A series of carboxylic anhydrides and acyl azides were synthesized using TsCl under ultrasound irradiation and conventional stirring with simple procedure, mild reaction conditions, high yields, and scale-up ability without any restriction. In most cases, the reaction under ultrasound irradiation was better in both yields and the reaction times compared to the conventional method. Conclusion: A convenient method has been developed for the preparation of carboxylic anhydrides and acyl azides under ultrasound irradiation and conventional stirring. The present method is practical and a highly effective alternative for previous reports. The major advantages of this method are: (i) simplicity of the procedure (ii) high yields and high purity of product (iii) scale-up capacity without considerable limitation in conventional system. Under ultrasound irradiation short reaction times as compared to conventional method are observed; yields are comparable to or better than conventional method.
- Eskandari, Parvin,Kazemi, Foad
-
p. 431 - 439
(2017/07/24)
-
- Pathways in the Degradation of Geminal Diazides
-
The degradation of geminal diazides is described. We show that diazido acetates are converted into tetrazoles through the treatment with bases. The reaction of dichloro ketones with azide anions provides acyl azides, through in situ formation of diazido ketones. We present experimental and theoretical evidence that both fragmentations may involve the generation of acyl cyanide intermediates. The controlled degradation of terminal alkynes into amides (by loss of one carbon) or ureas (by loss of two carbons) is also shown.
- Holzschneider, Kristina,H?ring, Andreas P.,Haack, Alexander,Corey, Daniel J.,Benter, Thorsten,Kirsch, Stefan F.
-
p. 8242 - 8250
(2017/08/14)
-
- The challenge of palladium-catalyzed aromatic azidocarbonylation: From mechanistic and catalyst deactivation studies to a highly efficient process
-
Azidocarbonylation of iodoarenes with CO and NaN3, a novel Heck-type carbonylation reaction, readily occurs in an organic solvent-H 2O biphasic system to furnish aroyl azides at room temperature and 1 atm. The reaction is catalyzed by Xantphos-Pd and exhibits high functional group tolerance. The catalyst deactivation product, [(Xantphos)PdI2], can be reduced in situ with PMHS to Pd(0) to regain catalytic activity. In this way, the catalyst loading has been lowered to 0.2% without any losses in selectivity at nearly 100% conversion to synthesize a series of aroyl azides in 80-90% isolated yield on a gram scale. Alternatively, the ArCON3 product can be used without isolation for further transformations in situ, e.g., to isocyanates, ureas, benzamides, and iminophosphoranes. A detailed experimental and computational study has identified two main reaction pathways for the reaction. For both routes, Ar-I oxidative addition to Pd(0) is the rate-determining step. In the presence of CO in excess, the Ar-I bond is activated by the less electron-rich Pd center of a mixed carbonyl phosphine complex. Under CO-deficient conditions, a slightly lower energy barrier pathway is followed that involves Ar-I oxidative addition to a more reactive carbonyl-free (Xantphos)Pd0 species. Mass transfer in the triphasic liquid-liquid-gas system employed for the reaction plays an important role in the competition between these two reaction channels, uniformly leading to a common aroyl azido intermediate that undergoes exceedingly facile ArCO-N 3 reductive elimination. Safety aspects of the method have been investigated.
- Miloserdov, Fedor M.,McMullin, Claire L.,Belmonte, Marta Martinez,Benet-Buchholz, Jordi,Bakhmutov, Vladimir I.,Macgregor, Stuart A.,Grushin, Vladimir V.
-
supporting information
p. 736 - 752
(2014/03/21)
-
- Orthogonal reactivity of acyl azides in C-H activation: Dichotomy between C-C and C-N amidations based on catalyst systems
-
The dual reactivity of acyl azides was utilized successfully in C-H activation by the choice of catalyst systems: while selective C-C amidation was achieved under thermal Rh catalysis, a Ru catalyst was found to mediate direct C-N amidation also highly se
- Shin, Kwangmin,Ryu, Jaeyune,Chang, Sukbok
-
supporting information
p. 2022 - 2025
(2014/05/06)
-
- Direct and facile synthesis of acyl azides from carboxylic acids using the trichloroisocyanuric acid-triphenylphosphine system
-
A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using a safe and inexpensive mixed reagent, trichloroisocyanuric acid-triphenylphosphine, is described.
- Akhlaghinia, Batool,Rouhi-Saadabad, Hamed
-
p. 181 - 185
(2013/05/09)
-
- Copper-mediated amidation of alkenylzirconocenes with acyl azides: Formation of enamides
-
Copper-mediated amidation of alkenylzirconocenes generated in situ from alkynes and zirconocenes with acyl azides is accomplished under mild conditions. The reaction can be used to prepare various enamides.
- Liu, Hailan,Zhou, Yiqing,Yan, Xiaoyu,Chen, Chao,Liu, Qingbin,Xi, Chanjuan
-
supporting information
p. 5174 - 5177
(2013/11/06)
-
- Design and synthesis of novel stiripentol analogues as potential anticonvulsants
-
A series of stiripentol (STP) analogues namely, 2-[(1E)-1-(1,3-benzodioxol- 5-yl)-4,4-dimethylpent-1-en-3-ylidene]-N-(aryl/H)hydrazinecarboxamides 7a-h, (±)-(5RS)-N-(aryl/H)-(1,3-benzodioxol-5-yl)-3-tert-butyl-4, 5-dihydro-1H-pyrazole-1-carboxamides (±)-8a-h, and (±)-[(5RS)-(1, 3-benzodioxol-5-yl)-3-tert-butyl-4,5-dihydro-1H-pyrazol-1-yl](aryl)methanones (±)-13a-f was synthesized by adopting appropriate synthetic routes and was pharmacologically evaluated in the preliminary anticonvulsant screens. The selected bioactive new chemical entities were subjected to ED50 determination and neurotoxicity evaluation. The most active congeners are 7h in MES screen and (±)-13b in scPTZ screen which displayed ED50 values of 87 and 110 mg/kg, respectively, as compared to that of STP (ED 50 = 277.7 and 115 mg/kg in MES and scPTZ, respectively).
- Aboul-Enein, Mohamed N.,El-Azzouny, Aida A.,Attia, Mohamed I.,Maklad, Yousreya A.,Amin, Kamilia M.,Abdel-Rehim, Mohamed,El-Behairy, Mohammed F.
-
p. 360 - 369
(2012/03/11)
-
- Palladium-catalyzed aromatic azidocarbonylation
-
Aryl iodides smoothly react with NaN3 and CO in the presence of a Pd/Xantphos catalyst to give aroyl azides (ArCON3) in 75-92 % yield. The reaction occurs under mild reaction conditions (1 atm, 20-50 °C) and exhibits high functional-group tolerance. (Xantphos=9,9-dimethyl-4,5- bis(diphenylphosphino)xanthene)
- Miloserdov, Fedor M.,Grushin, Vladimir V.
-
supporting information; experimental part
p. 3668 - 3672
(2012/05/20)
-
- Application of 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium tetrafluoroborate (TBTU) for the synthesis of acid azides
-
Conversion of acids to acyl azides using peptide coupling agent TBTU has been demonstrated. The procedure is simple and applicable to a range of carboxylic acids under mild reaction conditions. The protocol is extended to the synthesis of urethane protect
- Naik, Shankar A.,Lalithamba,Sureshbabu, Vommina V.
-
scheme or table
p. 103 - 109
(2011/04/15)
-
- FeCl36H2O-Catalyzed acceleration of the acylation of sodium azide with n-acylbenzotriazoles
-
Catalyzed by ferric chloride hexahydrate (FeCl36H2O), the acylation of sodium azide with N-acylbenzotriazoles was greatly accelerated in a mixed solvent of acetone and water. Thus, good to excellent yields of a variety of acyl azides were obtained at room temperature in a short time. Furthermore, because of the complete conversion of N-acylbenzotriazoles and the easy removal of the by-product, purification by column chromatography was no longer required, which made the protocol suitable for large-scale preparation.
- Zhong, Zhiyun,Hu, Jieling,Wang, Xiaoxia,Liu, Junhua,Zhang, Longfeng
-
experimental part
p. 2461 - 2467
(2011/08/05)
-
- T3P (propylphosphonic anhydride) mediated conversion of carboxylic acids into acid azides and one-pot synthesis of ureidopeptides
-
A general, mild, efficient, and environmentally benign protocol, which makes use of T3P as an acid activating agent for the direct synthesis of acid azides from carboxylic acids is described. Further, the protocol is employed for the one-pot synthesis of α-ureidopeptides starting from N-protected α-amino acids.
- Basavaprabhu,Narendra,Lamani, Ravi S.,Sureshbabu, Vommina V.
-
experimental part
p. 3002 - 3005
(2010/07/10)
-
- Facile one step synthesis of acyl azides and Nα-Fmoc/Boc/Z protected amino acid azides employing benzotriazole-1-yl-oxy-tris- (dimethylamino)-phosphonium hexafluorophosphate (BOP)
-
A simple route for the preparation of acyl azides from the corresponding carboxylic acids employing the peptide-coupling agent BOP is described. The procedure is simple, clean and high yielding. The chemistry is also extended to the preparation of several urethane protected amino acid azides (eight examples) as well.
- Vasantha,Sureshbabu, Vommina V.
-
experimental part
p. 812 - 817
(2011/01/04)
-
- Direct synthesis of acyl azides from carboxylic acids using 2-azido-l,3-dimethylimidazolinium chloride
-
Acyl azides were directly synthesized from carboxylic acids by the treatment with 2-azido-l,3-dimethylimidazolinium chloride (ADMC, 1) and amine. This procedure resulted in acyl azides in good yields and was applied to the amidation of amino acid derivatives without racemization of the products.
- Kitamura, Mitsuru,Tashiro, Norifumi,Takamoto, Yusuke,Okauchi, Tatsuo
-
scheme or table
p. 731 - 733
(2011/01/08)
-
- Direct synthesis of acyl azides from carboxylic acids by the combination of trichloroacetonitrile, triphenylphosphine and sodium azide
-
Various carboxylic acids were converted into acyl azides in excellent yields by treating with trichloroacetonitrile, triphenylphosphine and sodium azide at room temperature. The reaction was applicable to the preparation of dipeptide without rearrangement.
- Kim, Joong-Gon,Jang, Doo Ok
-
experimental part
p. 2072 - 2074
(2009/04/07)
-
- Direct, facile synthesis of acyl azides and nitriles from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride
-
A mild, efficient, and practical method for the one-step synthesis of acyl azides from carboxylic acids using bis(2-methoxyethyl)aminosulfur trifluoride is described. The reaction was easily extended to the synthesis of the corresponding nitriles by the inclusion of phosphorous reagents. The method can be applied to the synthesis of optically active nitriles in high yields, and is compatible with fluorous phosphines.
- Kangani, Cyrous O.,Day, Billy W.,Kelley, David E.
-
p. 5933 - 5937
(2008/02/10)
-
- Synthesis and biological activity of some novel N-aryl-nprime;-[5-(pyrid-4- yl)-1,3,4-thiadiazol-2-yl]ureas
-
With the aim of searching for biologically active urea compounds, a series of new N-aryl-N'-[5-(pyrid-4-yl)-1,3,4-thiadiazol-2-yl]ureas have been designed and synthesized. Their structures were confirmed by IR, 1H NMR, and elemental analysis. The crystal
- Song, Xin-Jian,Tan, Xiao-Hong,Wang, Yan-Gang
-
p. 1907 - 1913
(2008/02/10)
-
- Preparation of polyfunctional acyl azides
-
(Chemical Equation Presented) A general synthesis of acyl azides from the corresponding N-acyl benzotriazoles is described. The procedure affords acyl azides in good yields and avoids the use of acid activators and NO+ equivalents typically emp
- Katritzky, Alan R.,Widyan, Khalid,Kirichenko, Kostyantyn
-
p. 5802 - 5804
(2008/02/09)
-
- Preparation of acyl azides from aromatic carboxylic acids using triphosgene in ionic liquids
-
Acyl azides are obtained in high yields from aromatic carboxylic acids and sodium azide at room temperature in ionic liquids using triphosgene as a synthetic auxiliary under mild reaction conditions and with a short reaction time.
- Bao, Weiliang,Wang, Qiang
-
p. 700 - 701
(2007/10/03)
-
- A mild and efficient method for the preparation of acyl azides from carboxylic acids using triphosgene
-
An efficient use of triphosgene for the preparation of various acyl azides from carboxylic acids and sodium azide is described.
- Gumaste,Bhawal,Deshmukh
-
p. 1345 - 1346
(2007/10/03)
-
- Preparation of N-substituted aryl and alkyl carbamates and their inhibitory effect on oat seed germination.
-
A series of N-substituted aryl and alkyl carbamates (RNHCOOR'; R: aryl, alkyl; R': aryl, alkyl) was prepared and screened for inhibitory activity toward the germination of oat seeds. The activity of each compound was compared with that of chlorpropham (isopropyl 3-chlorocarbanilate). Some of the synthetic carbamates possessing the N-(phenylthio)methyl group, PhSCH2NHCOOR', showed inhibitory activity close or comparable to that of chlorpropham.
- Alizadeh, Babak Heidary,Sugiyama, Takeyoshi,Oritani, Takayuki,Kuwahara, Shigefumi
-
p. 422 - 425
(2007/10/03)
-
- Reinterpretation of curved hammett plots in reaction of nucleophiles with aryl benzoates: Change in rate-determining step or mechanism versus ground-state stabilization
-
A kinetic study is reported for the reaction of the anionic nucleophiles OH-, CN-, and N3- with aryl benzoates containing substituents on the benzoyl as well as the aryloxy moiety, in 80 mol % H2O-20 mol % dimethyl sulfoxide at 25.0 °C. Hammett log k vs σ plots for these systems are consistently nonlinear. However, a possible traditional explanation in terms of a mechanism involving a tetrahedral intermediate with curvature resulting from a change in rate-determining step is considered but rejected. The proposed explanation involves ground-state stabilization through resonance interaction between the benzoyl substituent and the electrophilic carbonyl center in the two-stage mechanism. Accordingly, the data are nicely accommodated on the basis of the Yukawa-Tsuno equation, which gives linear plots for all three nuceophiles. Literature reports of the mechanism of acyl transfer processes are reconsidered in this light.
- Um, Ik-Hwan,Han, Hyun-Joo,Ahn, Jung-Ae,Kang, Swan,Buncel, Erwin
-
p. 8475 - 8480
(2007/10/03)
-
- Lithium/DTBB-induced reduction of N-alkoxyamides and acyl azides
-
A series of N-alkoxyamides and N-methoxy-N-methylamides (Weinreb amides) have been subjected to dealkoxylation by reductive cleavage of the N-O bond with lithium powder and a catalytic amount of DTBB (10 mol%) at room temperature, leading to the corresponding amides. When the reaction is performed under reflux conditions, the corresponding alkanes, resulting from a formal deaminocarbonylation process, are obtained. This methodology applied to acyl azides furnished the corresponding primary amides.
- Yus, Miguel,Radivoy, Gabriel,Alonso, Francisco
-
p. 914 - 918
(2007/10/03)
-
- A new facile and rapid synthesis of acyl azides under solvent-free conditions
-
A rapid and simple method for the preparation of acyl azides is described. The reaction is carried out under solvent-free conditions from the reaction of acid chlorides with sodium azide supported on silica gel.
- Mallakpour,Hajipour,Vahabi
-
p. 1234 - 1235
(2007/10/03)
-
- ONE-FLASK SYNTHESIS OF ACYL AZIDES FROM CARBOXYLIC ACIDS; A FACILE ROUTE TO IMINOPHOSPHORANES
-
Carboxylic acids react with a mixture of N-chlorosuccinimide, triphenylphosphine and sodium azide at -30 deg C to form acyl azides in high yields.When two equivalents of triphenylphosphine are applied and the temperature allowed to raise, the reaction yields directly α-carbonyl stabilized iminophosphoranes via Staudinger reaction of the phosphine with the intermediate acyl azide.Key words: Iminophosphoranes; acyl azides; one-flask synthesis.
- Froeyen, Paul
-
-
- A PARTICULARLY CONVENIENT ONE-POT SYNTHESIS OF N-ALKOXYCARBONYL, N-ACYL AND N-AROYL SUBSTITUTED IMINOPHOSPHORANES; IMPROVED PREPARATION OF AZIDOFORMATES, AROYL AND ALKANOYL AZIDES; AN ALTERNATIVE ROUTE TO COMPLEX AMIDES
-
Chloroformates and acid chlorides react smoothly with sodium azide in acetone at 0 deg C, forming azidoformates, aroyl and alkanoyl azides in very high yield.With triphenylphosphine or other phosphines present in the reaction mixture, the forming azides are intercepted, leading directly to the corresponding N-alkanoyl, N-aroyl, N-alkoxycarbonyl, and N-aryloxycarbonyliminophosphoranes.N-acyliminophosphoranes react with n-butyllithium forming anions which react readily with electrophiles, e.g., carbonyl compounds, forming highly substituted iminophosphoranes.The phosphonium group is effortlessly removed from the latter compounds by acid hydrolysis forming the corresponding amides in high yield.Key words: Synthesis; iminophosphoranes; aroyl azides; alkanoyl azides; complex amides.
- Froeyen, Paul
-
p. 161 - 172
(2007/10/02)
-
- Synthesis of acyl azides via polymer-supported reagent
-
Acyl azides have been synthesised in high yields and in a state of high purity by reacting acyl chloride with polymer-supported azide ion reagent.
- Thorat, M. T.,Mane, R. B.,Deshmukh, J. G.,Salunkhe, M. M.,Wadgaonkar, P. P.
-
p. 186 - 187
(2007/10/02)
-
- Heteroacyl Azides as Acylating Agents for Aromatic or Heteroatomic Amines (1)
-
The possibility of formation of substituted heterocyclic amides from heteroacyl azides and aromatic or heteroatomic amines was investigated.Although acylation proceeded in some cases under mild reaction conditions, formation of N,N'-disubstituted ureas was the main process at elevated temperatures.
- Stanovnik, B.,Tisler, M.,Golob, V.,Hvala, I.,Nikolic, O.
-
p. 733 - 736
(2007/10/02)
-