35573-36-5

Upstream product

• 6132-45-2 ethyl 4-nitrophenyl carbonate 
• 2393-23-9 4-methoxy-benzylamine 
• 22719-86-4 1-(4-ethoxycarbonyloxy-phenyl)-ethanone 
• 22719-89-7 ethyl m-nitrophenyl carbonate 
• 78725-90-3 S-phenyl-O-ethyl thiolcarbonate 
• 107701-35-9 O-ethyl S-(4-chlorophenyl) thiocarbonate 
• 78725-88-9 O-ethyl S-(4-methylphenyl) thiocarbonate 
• 263746-53-8 O-ethyl-S-(4-bromophenyl)thiocarbonate 
• 541-41-3 chloroformic acid ethyl ester 
• 123-11-5 4-methoxy-benzaldehyde 
• 51-79-6 urethane 
• 27374-25-0 [(1-Ethoxycyclopropyl)oxy]trimethylsilane 
• 70978-37-9 1-(azidomethyl)-4-methoxybenzene 

Downstream Products

• 23304-25-8 p-methoxyphenyldiazomethane 
• 52646-45-4 p-methoxybenzyl 7β-(2-thienylacetamido)-3-(acetoxymethyl)-3-cephem-4-carboxylate 

Relevant academic research and scientific papers

The direct reductive amination of electron-deficient amines with aldehydes: The unique reactivity of the Re2O7 catalyst

An unprecedented direct reductive amination of electron-deficient amines such as Cbz-, Boc-, EtOCO-, Fmoc-, Bz-, ArSO2-, Ar2PO-, etc. protected amines with aldehydes is achieved using the Re2O 7 catalyst and silanes as the hydride source. Excellent regioselective mono-alkylation and chemoselective reductive-amination were observed.

Reactions of cyclopropanone acetals with alkyl azides: Carbonyl addition versus ring-opening pathways

(Chemical Equation Presented) The Lewis acid-mediated reactions of substituted cyclopropanone acetals with alkyl azides were found to strongly depend on the structure of the ketone component. When cyclopropanone acetal was treated with alkyl azides, N-substituted 2-azetidinones and ethyl carbamate products were obtained, arising from azide addition to the carbonyl, followed by ring expansion or rearrangement, respectively. When 2,2-dimethylcyclopropanone acetals were reacted with azides in the presence of BF3· OEt2, the products obtained were α-amino-α′- diazomethyl ketones, which arose from C2-C3 bond cleavage of the corresponding cyclopropanone, giving oxyallyl cations that were captured by azides. Aryl-substituted cyclopropanone acetals, when subjected to these conditions, afforded [1,2,3]oxaborazoles exclusively, which were also the result of C2-C3 bond rupture, azide capture, and then loss of nitrogen. In the reactions of n-hexyl-substituted cyclopropanone acetals with alkyl azides, a mixture of 2-azetidinones and regioisomeric [1,2,3]-oxaborazoles was obtained. The reasons for the different behavior of the various systems are discussed.

Kinetics and mechanism of the aminolysis of O-ethyl S-aryl thiocarbonates in acetonitrile

The Kinetics and mechanism of the reactions of O-ethyl S-(Z)aryl thiocarbonates with (X)benzylamines in acetonitrile at 45.0 °C are studied. Relatively small values of βx (βnuc) = 0.6 to approximately 0.8 and βz (βlg) = -0.5 to approximately -0.7 together with a negative cross-interaction constant ρxz (= -0.47) and failure of the reactivity-selectivity principle (RSP) are interpreted to indicate a concerted mechanism. The normal kinetic isotope effects (kH/kD = 1.3 to approximately 1.8) involving deuterated benzylamine nucleophiles suggest a hydrogen-bonded, four-center-type transition state.

Kinetics and mechanism of the aminolysis of ethyl aryl carbonates in acetonitrile

The aminolysis reactions of ethyl aryl carbonates with benzylamines in acetonitrile at 25.0°C are investigated. The base-catalyzed path, k2, disappears when strong nucleophiles (X = p-CH3O and p-CH3) react with a substrate activated by a strong nucleofuge (Z = p-NO2). The large magnitude of ρ(x) (-1.7 to -2.5), ρ(z) (3.4 to 4.3), and ρ(xz) (1.4) values, and relatively large k(H)/k(D) (1.6 to 1.8) found for the uncatalyzed path (k1) can be accounted for in terms of a stepwise mechanism with rate-limiting expulsion of the phenoxide leaving group. The catalyzed process (k2) is characterized by the much smaller magnitude of ρ(x) (-1.0 to -1.7), ρ(z) (0.4 to 0.7), and ρ(xz) (0.2), the larger k(H)/k(D) (2.1 to 2.5) values, and the lower ΔH(+) values (1.8-1.9 kcal mol-1) than those of the uncatalyzed process (k1) with large negative ΔS(+) values (-65 to -67 cal K-1 mol- 1). These results are consistent with four- and six-centered transition states for the two processes, k1 and k2, respectively.

Intermediate useful in the synthesis of pesticidal uracils

The compound 1 -methyl-6-trifluoromethyl-2,4(1H,3H)-pyrimidinedione is a novel compound useful in the preparation of pesticidal uracils. A route to the compound is disclosed, as is its use to prepare a known herbicide.