84713-20-2

Usage

Uses

Used in Pharmaceutical Industry:
BENZYL-N-VINYLCARBAMATE is used as a reagent for the synthesis of CF3or -?CF2-?substituted tetrahydroquinolines, which are important compounds in the development of pharmaceuticals. These synthesized tetrahydroquinolines possess potential therapeutic properties and can be utilized in the creation of new drugs to treat various medical conditions.
Used in Chemical Research:
In the field of chemical research, BENZYL-N-VINYLCARBAMATE is employed as a reagent to explore the synthesis of novel compounds with unique properties. Its role in the formation of CF3or -?CF2-?substituted tetrahydroquinolines allows researchers to investigate the potential applications and characteristics of these newly synthesized molecules, contributing to the advancement of chemical knowledge and innovation.

Preparation

A 1-L flask was equipped with a variable speed pump, a mechanical stirrer, a temperature controller, a 4" (10 cm) column packed with ceramic saddles, a distillation head, a spiral condenser (cooled with water at 10–15 ℃), and a receiver. The flask was charged with toluene (150–200 mL) and phenothiazine (0.5 g) and the solution was heated to 105–110 ℃. The receiver was charged with benzyl alcohol (86 g, 0.8 mol), phenothiazine (0.05 g), and triethylamine (0.1–0.3 g). This mixture was cooled in ice and stirred. A solution of acryloyl azide (1 mol), prepared as described above, was pumped into the distillation flask over a period of 4–5 h, maintaining the pot temperature at 105–110 ℃ with a heating mantle. The vapor temperature varied, depending on the rate of addition of the azide, but was in the range 80–100 ℃. The distillate was passed directly into the benzyl alcohol mixture. After the addition of acryloyl azide, the distillation continued, generating a further 10–20 mL of toluene. The receiver was then removed from the distillation set-up, and its contents were stirred at 0–5 ℃ for 1– 2 h. The product mixture was then allowed to gradually warm to room temperature and was stirred until HPLC analysis indicated complete reaction. The mixture was then concentrated in vacuo to a weight of 200–250 g. The residue was treated with heptane (300–350 mL) and cooled to 15 ℃ with stirring. A few seed crystals of benzyl N-vinyl carbamate 810 were added, and the mixture was stirred for 2–3 h. The product was collected by filtration, washed with heptane, and dried in vacuo. Yield 115–128 g (65–72%); mp 41–44 ℃.

Synthesis Reference(s)

The Journal of Organic Chemistry, 54, p. 4649, 1989 DOI: 10.1021/jo00280a036

InChI:InChI=1/C10H11NO2/c1-2-11-10(12)13-8-9-6-4-3-5-7-9/h2-7H,1,8H2,(H,11,12)

Upstream product

• 3555-94-0 isocyanatoethene 
• 100-51-6 benzyl alcohol 
• 1145-80-8 N-(benzyloxycarbonyl)-L-serine 
• 501-53-1 benzyl chloroformate 
• 50830-56-3 acryloyl azide 
• 105-57-7 diethyl acetal 
• 621-84-1 O-benzyl carbamate 
• 34325-66-1 vinyl-carbamic acid 

Downstream Products

• 893409-14-8 (6-Ethyl-1,3-dimethyl-4,5,6,7-tetrahydro-1H-pyrazolo[3,4-b]pyridine-4-yl)-carbamic acid benzyl ester 
• 474645-96-0 (2R,4S)-(2-ethyl-6-trifluoromethyl-1,2,3,4-tetrahydroquinolin-4-yl)carbamic acid benzyl ester 
• 887475-73-2 C₁₇H₁₈N₄O₂S 
• 887475-72-1 C₁₇H₁₈N₄O₂S 
• 82353-55-7 benzyl (S)-1-oxopropan-2-ylcarbamate 
• 1201905-42-1 benzyl 2-((5R,6S)-5-(tert-butyldimethylsilyloxy)-6-hydroxycyclohex-1-enyl)ethylcarbamate 
• 1257051-27-6 benzyl 2-((5R,6R)-5-(tert-butyldimethylsilyloxy)-6-(3-(2,2-dimethoxyethyl)-2-iodo-6-methoxyphenoxy)cyclohex-1-enyl)ethylcarbamate 
• 1201905-44-3 benzyl N-[2-[(5aR,6R,9aS)-6-(tert-butyldimethylsilyloxy)-6,7-dihydro-1-(2,2-dimethoxyethyl)-4-methoxy-9a(5aH)-dibenzofuranyl]ethyl]carbamate 
• 1197815-35-2 C₂₅H₂₇ClN₂O₃ 

Relevant academic research and scientific papers

An improved process for the preparation of benzyl-N-vinyl carbamate

An improved method that can be easily scaled up has been developed for the preparation of benzyl-N-vinyl carbamate. In this method vinyl isocyanate formed by the Curtius rearrangement of acryloyl azide is codistilled with a solvent such as toluene into benzyl alcohol containing a catalyst and inhibitor. The product thus obtained can be purified by crystallization, avoiding purification by high-vacuum distillation or chromatography. Potential safety issues associated with the process are discussed.

A Boronic Acid Conjugate of Angiogenin that Shows ROS-Responsive Neuroprotective Activity

Angiogenin (ANG) is a human ribonuclease that is compromised in patients with amyotrophic lateral sclerosis (ALS). ANG also promotes neovascularization, and can induce hemorrhage and encourage tumor growth. The causal neurodegeneration of ALS is associated with reactive oxygen species, which are also known to elicit the oxidative cleavage of carbon–boron bonds. We have developed a synthetic boronic acid mask that restrains the ribonucleolytic activity of ANG. The masked ANG does not stimulate endothelial cell proliferation but protects astrocytes from oxidative stress. By differentiating between the two dichotomous biological activities of ANG, this strategy could provide a viable pharmacological approach for the treatment of ALS.

INHIBITING DEUBIQUITINASE USP25 AND USP28

The present disclosure relates to modulators, such as inhibitors, of at least one pathway chosen from USP28 and USP25, pharmaceutical compositions comprising the inhibitors, and methods of using the inhibitors. The modulators, such as inhibitors, of at least one pathway chosen from USP28 and USP25 can be useful in the treatment of cancers, among other ailments. The present disclosure provides compounds of Formula (I).

ANGIOGENIN-BORONIC ACID CONJUGATES WITH SELECTIVE NEUROPROTECTION ACTIVITY

Masked h-ANG variant conjugates useful for protection of cells, particularly neuronal cells from injury and death, particularly from injury and death associated with ROS (reactive oxygen species). Masked h-Ang variant conjugates do not exhibit ribonucleolytic activity until unmasked. Masked h-ANG variant conjugates are activatable by reaction with ROS and exhibit ribonucleolytic activity only after reaction with ROS. Masked h-ANG variant conjugates are useful in the treatment of neurodegenerative diseases and disorders, such as amyotrophic lateral sclerosis. Certain h-ANG variants in which lysine at position 40 is replaced with cysteine are provided at least as starting materials for making masked h-ANG variant conjugates. Certain h-ANG variants in which lysine at position 40 is replaced with thialysine are generated on unmasking of h-ANG variant conjugates and exhibit ribonucleolyitc activity.

A process for the preparation and synthetic ChondriamideA and ChondriamideC method (by machine translation)

The invention provides a process for the preparation of synthetic Chondriamide A and Chondriamide C and method, wherein the invention provides a process for the preparation, including: formula (I) compounds of structure, palladium catalyst, phosphorus ligand, alkali and organic solvent at room temperature the illumination reaction, formula (II) structure obtained olefin; wherein through the selection of a particular phosphorus ligand; make the method of the invention can be under the photocatalysis, room temperature to realize high-efficient catalytic conversion, and the mild reaction conditions, simple operation, in line with the development of green environment-friendly chemical requirements, and the range of choice of substrate and functional group compatibility has more universal, and has outstanding chemical selectivity; and the method can be successfully applied to complex molecular introducing carbon-carbon double bond to the programme, to optimize a part of the drug molecular synthesis strategy, improve the synthesis efficiency, reduce the cost, with industrial synthetic value and prospects. (by machine translation)

Lewis Acid Catalyzed [3+2] Coupling of Quinone Monoacetals or Quinone Imine Ketals with Vinylcarbamates

A mild and concise [3+2] coupling of quinone monoacetals or quinone imine ketals with vinylcarbamates promoted by Lewis acid was realized. Various 2-carbamate-2,3-dihydrobenzofurans and 2-carbamate-indolines have been prepared in moderate to good yields.

Photoredox-induced three-component Oxy-, Amino-, and Carbotrifluoromethylation of enecarbamates

A photoredox-catalzyed trifluoromethylation of enecarbamates process is reported. This pathway uses Togni's reagent as the CF3 source and follows a radical/cationic pathway. Under the optimized conditions using [Ru(bpy)3(PF6)2] as the photocatalyst, a wide range of substituted enecarbamates can readily be difunctionalized by means of various O, N, and C nucleophiles.

Highly enantioselective synthesis of cyclopropylamine derivatives via Ru(II)-pheox-catalyzed direct asymmetric cyclopropanation of vinylcarbamates

The Ru(II)-Pheox-catalyzed asymmetric cyclopropanation of vinylcarbamates with diazoesters resulted in the corresponding cyclopropylamine derivatives in high yield and excellent diastereoselectivity (up to 96:4) and enantioselectivity (up to 99% ee).

N-(1-Acylaminoalkyl)amidinium salts derived from DBU or related bases as reactive intermediates in α-amidoalkylation reactions

1-(N -Acylamino)alkyltriphenylphosphonium salts 4, when treated with DBU, DBN or TBD in CD3 CN or MeCN, were transformed immediately into the corresponding 1-(N- acylamino)alkylamidinium or guanidinium salts 5. Salts 5 with a proton at the α-position underwent slow transformation to the corresponding enamides 6. 1-(N- Acylamino)alkyltriphenylphosphonium salts 4, amidinium or guanidinium salts 5, as well as enamides 6 reacted readily with β-dicarbonyl compounds in the presence of corresponding base under microwave irradiation at 60 °C to give the expected product of α-amidoalkylation of the enolate anion. The role of 1-(N-acylamino) alkylamidinium or guanidinium salts 5 as reactive intermediates in α-amidoalkylation with 1-(N-acylamino)alkyltriphenylphosphonium salts is discussed. ARKAT-USA, Inc.

Formal homo-nazarov and other cyclization reactions of activated cyclopropanes

The Nazarov cyclization of divinyl ketones gives access to cyclopentenones. Replacing one of the vinyl groups by a cyclopropane leads to a formal homo-Nazarov process for the synthesis of cyclohexenones. In contrast to the Nazarov reaction, the cyclization of vinyl-cyclopropyl ketones is a stepwise process, often requiring harsh conditions. Herein, we describe two different approaches for further polarization of the three-membered ring of vinyl-cyclopropyl ketones to allow the formal homo-Nazarov reaction under mild catalytic conditions. In the first approach, the introduction of an ester group α to the carbonyl on the cyclopropane gave a more than tenfold increase in reaction rate, allowing us to extend the scope of the reaction to non-electron-rich aryl donor substituents in the β position to the carbonyl on the cyclopropane. In this case, a proof of principle for asymmetric induction could be achieved using chiral Lewis acid catalysts. In the second approach, heteroatoms, especially nitrogen, were introduced β to the carbonyl on the cyclopropane. In this case, the reaction was especially successful when the vinyl group was replaced by an indole heterocycle. With a free indole, the formal homo-Nazarov cyclization on the C3 position of indole was observed using a copper catalyst. In contrast, a new cyclization reaction on the N1 position was observed with BrAnsted acid catalysts. Both reactions were applied to the synthesis of natural alkaloids. Preliminary investigations on the rationalization of the observed regioselectivity are also reported.