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            ‐Butyl Diazoacetate

Regitz, Manfred; Hocker, J.; Liedhegener, Annemarie

doi:10.1002/0471264180.os048.11

Cited by 33 publications

(41 citation statements)

References 18 publications

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“…The solvents (AR grade) were dried according to standard procedures. Diazo compounds N 2 CAr 2 (Ar = Ph, p-C 6 H 4 OMe, p-C 6 H 4 Me, p-C 6 H 4 Cl), [28] N 2 C(Ar)CO 2 R (R = Me, Ar = Ph, p-C 6 H 4 OMe, p-C 6 H 4 NO 2 ; R= Et, Ar = Ph; R = CH 2 CH=CH 2 , Ar = Ph), [29] (2E,4E)-2,4-hexadienyl (E)-2-diazo-4-phenyl-3-butenoate, [30] dimethyl diazomalonate, [31] and complexes [Ru(por)(CO)], [32] [Os(tpfpp)(CO)], [4a] [Fe(tpfpp)(CPh 2 )] (1 a-Fe), and [Fe(tpfpp)(CPh 2 )(MeIm)] (3 d-Fe) [2] were prepared by literature methods. UV/Vis spectra (in CH 2 Cl 2 ) were recorded on a HP 8453 Diode Array spectrophotometer, and IR spectra (KBr pellet) on a Bio-Rad FTS165 spectrometer.…”

Section: Methodsmentioning

confidence: 99%

Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

Huang

et al. 2004

Chemistry A European J

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A wide variety of ruthenium porphyrin carbene complexes, including [Ru(tpfpp)(CR(1)R(2))] (CR(1)R(2) = C(p-C(6)H(4)Cl)(2) 1 b, C(p-C(6)H(4)Me)(2) 1 c, C(p-C(6)H(4)OMe)(2) 1 d, C(CO(2)Me)(2) 1 e, C(p-C(6)H(4)NO(2))CO(2)Me 1 f, C(p-C(6)H(4)OMe)CO(2)Me 1 g, C(CH==CHPh)CO(2)CH(2)(CH==CH)(2)CH(3) 1 h), [Ru(por)(CPh(2))] (por=tdcpp 2 a, 4-Br-tpp 2 b, 4-Cl-tpp 2 c, 4-F-tpp 2 d, tpp 2 e, ttp 2 f, 4-MeO-tpp 2 g, tmp 2 h, 3,4,5-MeO-tpp 2 i), [Ru(por)[C(Ph)CO(2)Et]] (por=tdcpp 2 j, tmp 2 k), [Ru(tpfpp)(CPh(2))(L)] (L = MeOH 3 a, EtSH 3 b, Et(2)S 3 c, MeIm 3 d, OPPh(3) 3 e, py 3 f), and [Ru(tpfpp)[C(Ph)CO(2)R](MeOH)] (R = CH(2)CH==CH(2) 4 a, Me 4 b, Et 4 c), were prepared from the reactions of [Ru(por)(CO)] with diazo compounds N(2)CR(1)R(2) in dichloromethane and, for 3 and 4, by further treatment with reagents L. A similar reaction of [Os(tpfpp)(CO)] with N(2)CPh(2) in dichloromethane followed by treatment with MeIm gave [Os(tpfpp)(CPh(2))(MeIm)] (3 d-Os). All these complexes were characterized by (1)H NMR, (13)C NMR, and UV/Vis spectroscopy, mass spectrometry, and elemental analyses. X-ray crystal structure determinations of 1 d, 2 a,i, 3 a, b, d, e, 4 a-c, and 3 d-Os revealed Ru==C distances of 1.806(3)-1.876(3) A and an Os==C distance of 1.902(3) A. The structure of 1 d in the solid state features a unique "bridging" carbene ligand, which results in the formation of a one-dimensional coordination polymer. Cyclic voltammograms of 1 a-c, g, 2 a-d, g-k, 3 b-d, 4 a, b, and 3 d-Os show a reversible oxidation couple with E(1/2) values in the range of 0.06-0.65 V (vs Cp(2)Fe(+/0)) that is attributable to a metal-centered oxidation. The influence of carbene substituents, porphyrin substituents, and trans-ligands on the Ru==C bond was examined through comparison of the chemical shifts of the pyrrolic protons in the porphyrin macrocycles ((1)H NMR) and the M==C carbon atoms ((13)C NMR), the potentials of the metal-centered oxidation couples, and the Ru==C distances among the various ruthenium porphyrin carbene complexes. A direct comparison among iron, ruthenium, and osmium porphyrin carbene complexes is made.

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Section: Methodsmentioning

confidence: 99%

Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

Huang

et al. 2004

Chemistry A European J

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“…1,2 Under typical batch conditions, the diazo acceptor molecule is reacted with tosyl azide in the presence of a base, such as NEt3, DBU or K2CO3, at ambient temperature over a period of up to 24 hours. 3,4,28,[75][76][77] Reaction times longer than several hours can be difficult to achieve in tubular reactors, so we sought to optimize the continuous diazo transfer reaction over a short reaction time of 10 min (Table 1). It has previously been reported that the diazo transfer requires only catalytic quantities of base to proceed.…”

Section: Continuous Diazo Transfer Using Batch Prepared Tosyl Azidementioning

confidence: 99%

“…The preparation of sulfonyl azide diazo transfer reagents are hazardous procedures which require extreme care. 3,4,8,27,28,75 In a typical preparation of tosyl azide a solution of tosyl chloride in MeCN is added slowly to an aqueous solution of sodium azide. As the substitution reaction is exothermic, the reaction must be kept at 0 °C to prevent explosive decomposition of the heat sensitive tosyl azide.…”

Section: In Situ Generation and Use Of Tosyl Azidementioning

confidence: 99%

Taming tosyl azide: the development of a scalable continuous diazo transfer process

et al. 2016

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Heat and shock sensitive tosyl azide was generated and used on demand in a telescoped diazo transfer process. Small quantities of tosyl azide were accessed in a 'one pot' batch procedure using shelf stable, readily available reagents. For large scale diazo transfer reactions tosyl azide was generated and used in a telescoped flow process, to mitigate the risks associated with handling potentially explosive reagents on scale. The in situ formed tosyl azide was used to rapidly perform diazo tranfer to a range of acceptors, including β-ketoesters, β-ketoamides, malonate esters and β-ketosulfones. An effective in-line quench of sulfonyl azides was also developed, whereby a sacrificial acceptor molecule ensured complete consumption of any residual hazardous diazo transfer reagent. The telescoped diazo transfer process with in-line quenching was used to safely prepare over 21 g of an α-diazocarbonyl in >98% purity without any column chromatography.

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“…p-Toluenesulfonyl azide [46], 4-Bromo-2,6-bis(bromomethyl)anisole [47] and 4-bromo-2-methoxy-1,3-xylyl-18-crown-5 [20] were prepared as described previously.…”

Section: Synthesismentioning

confidence: 99%

Synthesis, properties and X‐ray structure of 5‐azido‐2‐methoxy‐1,3‐xylyl‐18‐crown‐5

Yonekawa¹,

Goodpaster²,

Abel³

et al. 2006

Journal of Heterocyclic Chem

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5-Azido-2-methoxy-1,3-xylyl-18-crown-5 has been prepared by reacting p-toluenesulfonyl azide with the carbanion generated from the reaction of 5-bromo-2-methoxy-1,3-xylyl-18-crown-5 with n-butyl lithium. The asymmetric N 3 stretch of this product has been observed as a single band at 2110 cm -1 in dichloromethane solution. Addition of solid NaSCN, KSCN and CsSCN shifts this band to 2115, 2113 and 2112 cm -1 , respectively. Computational studies of this azide at the B3LYP-6-31G* level in the presence and absence of Na + predicted these bands to be at 2173 cm -1 and 2184 cm -1. For the salt-containing solutions, additional bands were observed at 2066 cm -1 , 2056 cm -1 and 2055 cm -1 , respectively, which are in the range expected for CN stretches. The X-ray structure of this azide has been determined. The terminal and internal N-N bond lengths were found to be 1.127(2) and 1.245(2) , respectively, which is the usual pattern for aromatic azides. The crown ether is looped over the face of the aromatic ring resulting in an angle of 38.94° between the plane defined by the aromatic ring and that defined by the five ring oxygen atoms. In addition, the CH 3 group is rotated out of the plane of the phenyl ring with C1-C18-O181-C182 and C17-C18-O181-C182 dihedral angles of 93.81(14)° and -90.54(14)°, respectively.

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t ‐Butyl Diazoacetate

Abstract: t ‐Butyl diazoacetate intermediate: p ‐toluenesulfonyl azide solvent: 75.8 g. (0.75 mole) of previously distilled triethylamine intermediate: 92.6 (0.50 mole) of t ‐butyl α‐diazoacetoacetate … Show more

Cited by 33 publications

References 18 publications

Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

Spectral, Structural, and Electrochemical Properties of Ruthenium Porphyrin Diaryl and Aryl(alkoxycarbonyl) Carbene Complexes: Influence of Carbene Substituents, Porphyrin Substituents, and trans‐Axial Ligands

Taming tosyl azide: the development of a scalable continuous diazo transfer process

Synthesis, properties and X‐ray structure of 5‐azido‐2‐methoxy‐1,3‐xylyl‐18‐crown‐5

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