36016-38-3

Basic information

• Product Name: tert-Butyl N-hydroxycarbamate
• Synonyms: N-(T-BUTOXYCARBONYL)-HYDROXYLAMINE;N-T-BOC HYDROXYLAMINE;N-HYDROXYCARBAMIC ACID TERT-BUTYL ESTER;N-BOC-HYDROXYLAMINE;N-Boc-hydroxylamine, >=98%;N-tert-Butoxycarbonylhydroxylamine, 98+%;N-(tert-Butoxycarbonyl)hydroxylamine~tert-ButylN-hydroxycarbamate;TERT-BUTYL N-HYDROXYCARBAMATE 99.0%
• CAS NO: 36016-38-3
• Molecular Formula: C₅H₁₁NO₃
• Molecular Weight: 133.15
• EINECS: 252-836-2
• Product Categories: INTERMEDIATESOFMEROPENAM;API intermediates;Hydroxylamines;Hydroxylamines (N-Substituted);Naphthyridine,Quinoline
• Mol File: 36016-38-3.mol

Chemical Properties

• Melting Point: 53-55 °C(lit.)
• Boiling Point: 245.66°C (rough estimate)
• Flash Point: 105.2 °C
• Appearance: White to light pink/Crystalline Powder
• Density: 1.2510 (rough estimate)
• Vapor Pressure: 0.00344mmHg at 25°C
• Refractive Index: 1.4120 (estimate)
• Storage Temp.: 2-8°C
• Solubility: Chloroform, Methanol
• PKA: 9.31±0.23(Predicted)
• Water Solubility: Slightly soluble in water.
• Sensitive: Moisture Sensitive
• BRN: 1756546
• CAS DataBase Reference: tert-Butyl N-hydroxycarbamate(CAS DataBase Reference)
• NIST Chemistry Reference: tert-Butyl N-hydroxycarbamate(36016-38-3)
• EPA Substance Registry System: tert-Butyl N-hydroxycarbamate(36016-38-3)

Safety Data

• Safety Statements: 22-24/25
• WGK Germany: 3
• F: 21
• Hazardous Substances Data: 36016-38-3(Hazardous Substances Data)

Usage

Uses

Used in Pharmaceutical Industry:
t-Butyl N-hydroxycarbamate is used as a reagent for the synthesis of hydroxylamine derivatives, specifically t-butyl-N-(acyloxy)carbamates and N,O-diacylated N-hydroxyarylsulfonamides. These derivatives are essential in the development of new pharmaceutical compounds with potential therapeutic applications.
Used in Chemical Synthesis:
In the field of chemical synthesis, t-Butyl N-hydroxycarbamate is used in the preparation of azridines by cycloaddition of azides with nitroso Diels-Alder adducts. This process is crucial for the creation of complex molecular structures with potential applications in various industries, including pharmaceuticals, agrochemicals, and materials science.
Overall, t-Butyl N-hydroxycarbamate plays a significant role in the synthesis of various chemical compounds, particularly in the pharmaceutical industry, where its derivatives have the potential to contribute to the development of new therapeutic agents. Additionally, its application in chemical synthesis allows for the creation of complex molecular structures with a wide range of potential uses.

Synthesis Reference(s)

Journal of the American Chemical Society, 81, p. 955, 1959 DOI: 10.1021/ja01513a049Tetrahedron Letters, 24, p. 231, 1983 DOI: 10.1016/S0040-4039(00)81372-6

InChI:InChI=1/C5H11NO3/c1-5(2,3)9-4(7)6-8/h8H,1-3H3,(H,6,7)

Upstream product

• 1070-19-5 N-(tert-butyloxycarbonyl) azide 
• 24424-99-5 di-tert-butyl dicarbonate 
• 5470-11-1 hydroxylamine hydrochloride 
• 870-46-2 t-butoxycarbonylhydrazine 
• 24424-95-1 di-tert-butyl tricarbonate 
• 105340-85-0 (benzyloxy)carbamic acid 1,1-dimethylethyl ester 
• 31583-38-7 tert-butyl 1,4-dioxo-1,4-dihydro-3H-benzo[d][1,2]oxazine-3-carboxylate 
• 24608-52-4 tert-butyl chloroformate 
• 38965-26-3 3,3-Dimethylbuttersaeureanhydrid 

Downstream Products

• 85006-25-3 N,N-di(tert-butoxycarbonyl)hydroxylamine 
• 105340-85-0 (benzyloxy)carbamic acid 1,1-dimethylethyl ester 
• 99768-83-9 (acetyloxy)carbamic acid 1,1-dimethyl ethyl ester 
• 105838-14-0 tert-butyl N-tosyloxycarbamate 
• 38100-29-7 t-Butyl-N-(2,4,6-trinitrophenoxy)-carbamat 
• 58377-40-5 tert-butyl N-hydroxy-N-phenylcarbamate 
• 58377-41-6 tert.-Butyl-N-p-tert-butylphenyl-hydroxycarbamat 
• 58377-42-7 tert.-Butyl-N-m-nitrophenyl-hydroxycarbamat 
• 27868-41-3 N-tert-Butyloxycarbonyl-O-aethoxycarbonyl-hydroxylamin 
• 27268-72-0 4-cyclohexyl-[1,2,4]oxadiazolidine-3,5-dione 
• 27268-73-1 4-benzyl-[1,2,4]oxadiazolidine-3,5-dione 
• 35657-40-0 tert-butyl (pivaloyloxy)carbamate 
• 17508-16-6 tert-butyl (2,4-dinitrophenoxy)carbamate 
• 38100-27-5 t-Butyl-N-(2,6-dinitrophenoxy)-carbamat 

Relevant articles and documents

Enantioselective Diels-Alder reaction with an α-chloronitroso dienophile derived from 5-O-acetyl-2,3-isopropylidenedioxy-D-ribose

Crystalline 5-O-acetyl-2,3-isopropylidenedioxy-D-ribonolactone oxime (8) was synthesised from D-ribose in 40% overall yield. The chloronitroso dienophile 3b was obtained from 8 by oxidation with t-BuOCl and underwent asymmetric Diels-Alder reaction with cyclic and acyclic dienes 10-13 to give crystalline adducts 14a-17a in good yield and excellent enantiomeric excess (93-99%).

Stabilization of vesicular and supported membranes by glycolipid oxime polymers

We report herein new synthetic glycolipid dimers and polymers that provide unprecedented stability to both supported (SLBs) and vesicular lipid bilayers against dehydration and serum exposure. These novel physical properties will enable pharmaceutical delivery and development of SLB bioanalytical devices. The Royal Society of Chemistry.

Palladium-Catalyzed C-O Cross-Coupling as a Replacement for a Mitsunobu Reaction in the Development of an Androgen Receptor Antagonist

A scalable and efficient synthesis of N-{trans-4-[(8-cyanoquinolin-4-yl)oxy]cyclohexyl}-3-fluorobenzamide (BAY 1161116), an androgen receptor antagonist, is reported. The original synthesis included a low-yielding Mitsunobu reaction and employed cis-aminocyclohexanol, which is accessible only via a troublesome synthesis, as a key building block. The novel synthetic pathway starts from readily available trans-aminocyclohexanol and features a palladium-catalyzed etherification reaction in place of the Mitsunobu reaction as the key step. This four-step synthesis can be performed reliably on a multikilogram scale, and purification of all intermediates as well as the final product can be achieved by simple extraction and crystallization procedures.

Alternating Current Electrolysis as Efficient Tool for the Direct Electrochemical Oxidation of Hydroxamic Acids for Acyl Nitroso Diels–Alder Reactions

The acyl nitroso Diels–Alder reaction of 1,3-dienes with electrochemically oxidised hydroxamic acids is described. By using alternating current electrolysis, their typical electro-induced decomposition could be suppressed in favour of the 1,2-oxazine cycloaddition products. The reaction was optimised using Design of Experiments (DoE) and a sensitivity test was conducted. A mixture of triethylamine/hexafluoroisopropanol served as supporting electrolyte in dichloromethane, thus giving products of high purity after evaporation of the volatiles without further purification. The optimised reaction conditions were applied to various 1,3-dienes and hydroxamic acids, giving up to 96 % isolated yield.

Photo-auxiliary approach to control excited state reactivity: Cross [2+2]-photocycloaddition of oxazolidinone based hydrazides

Chiral oxazolidinone based hydrazides undergo efficient cross [2 + 2]-photocycloaddition upon visible light illumination. Oxazolidinone functionality acted as an energy harvesting photo-auxiliary. The cross [2 + 2]-photocycloaddition proceeded efficiently from the excited state with moderate to excellent isolated yield of the photoproduct. The photo-auxiliary can be conveniently removed post-photoreaction, which highlights the versatility of this strategy.

Palladium-Catalyzed Synthesis of Indolines from Aroyloxycarbamates through a Tandem Decarboxylative Amination/Heck/Annulation Reaction

A novel synthesis of functionalized indolines via a Pd-catalyzed tandem decarboxylative amination/Heck/annulation reaction has been developed. This process features operational simplicity, mild conditions, and the use of a readily available and environmentally friendly starting material, namely carboxylic acid. Furthermore, the reaction shows good functional group tolerance and chemical selectivity. (Figure presented.).

FMOC PROTECTED (2S)-2-AMINO-8-[(1,1-DIMETHYLETHOXY)AMINO]-8-OXO-OCTANOIC ACID, (S)-2-AMINO-8-OXONONANOIC ACID AND (S)-2-AMINO-8-OXODECANOIC ACID FOR PEPTIDE SYNTHESIS

The invention discloses Fmoc protected (2S)-2-amino-8-[(1,1- dimethylethoxy)amino]-8-oxo-octanoic acid, (S)-2-amino-8- oxononanoic acid and (S)-2-amino-8-oxodecanoic acid for use in peptide synthesis, such as solid phase synthesis, as well as the peptide H3K27 (Ac-Lys-Ala-Ala-Arg-Aox-Ser-Ala-NH2) prepared from Fmoc protected (2S)-2-amino-8-[(1,1-dimethylethoxy)amino]-8-oxo-octanoic acid (Aox). These three exemplary compounds as well as their unprotected forms are claimed in the form of four generic formulae. The first of these four formulae is (formula (I)) where -NPro is a protected amino group, such as an amino group protected with a base-labile protecting group, -L- is alkylene, heteroalkylene, arylene or aralkylene, -X- is a covalent bond, -N(H) - or -N(RN)-, where -RN is alkyl, -R2 is hydrogen or alkyl, -R3 is alkyl, such as C2-10 alkyl, or heterocyclyl, and -LAA- and -R1 are as defined in the claims.

An Effective Method for the Synthesis of 1,3-Dihydro-2H-indazoles via N-N Bond Formation

The [4+1] cycloaddition reaction of bifunctional amino reagents has been achieved with in situ formed aza-ortho-quinone methides. Specifically, N-(tosyloxy)carbamates were used as an N1 synthon and bifunctional amino reagents for this transformation, which provides a metal-free, catalyst-free, and oxidant-free strategy to form nitrogen-nitrogen bonds. (Figure presented.).

Base-Mediated Intramolecular Decarboxylative Synthesis of Alkylamines from Alkanoyloxycarbamates

A general and effective method for the synthesis of alkylamine via intramolecular decarboxylation of alkanoyloxycarbamates is described. The alkanoyloxycarbamates are readily prepared with alkyl carboxylic acids and hydroxylamine. The reaction shows a broad range of substrates (primary and secondary alkyl) with functional tolerance, and the corresponding products were obtained in good yields under mild conditions.

Synthesis of indoles from aroyloxycarbamates with alkynes: Via decarboxylation/cyclization

An efficient Pd-catalyzed decarboxylation/cyclization of aroyloxycarbamates to realize substituted indoles has been disclosed. Terminal alkynes as the coupling partners lead to site specific 2-substituted indoles through two pathways, while internal alkynes with aroyloxycarbamates can be transformed to 2,3-disubstituted indoles directly. This protocol is further demonstrated by the efficient synthesis of indoles as well as the success of employing inexpensive aryl acids as starting materials to construct C-N bonds by releasing CO2.