14602-86-9

Basic information

• Product Name: (-)-MENTHYL CHLOROFORMATE
• Synonyms: MCF;(-)-MENTHYL CHLOROFORMATE;(-)-CHLOROFORMYLOXY-P-MENTHANE;(1R,2S,5R)-(-)-MENTHYLCHLOROFORMATE;(-)-(1R)-MENTHYL CHLOROFORMATE;(1R)-(-)-MENTHYL CHLOROFORMATE;Chloroformic acid (1R)-menthyl ester~L-Menthyl chloroformate;L-p-menth-3-yl chloroformate
• CAS NO: 14602-86-9
• Molecular Formula: C₁₁H₁₉ClO₂
• Molecular Weight: 218.72
• EINECS: 1312995-182-4
• Product Categories: CHLOROFORMATES;chiral;Biochemistry;for Resolution of Alcohols & Thiols;for Resolution of Bases;Monocyclic Monoterpenes;Optical Resolution;Synthetic Organic Chemistry;Terpenes
• Mol File: 14602-86-9.mol

Chemical Properties

• Boiling Point: 108-109 °C11 mm Hg(lit.)
• Flash Point: 158 °F
• Appearance: /
• Density: 1.031 g/mL at 20 °C(lit.)
• Vapor Pressure: 0.01 psi ( 20 °C)
• Refractive Index: n20/D 1.459
• Storage Temp.: 2-8°C
• Sensitive: Moisture Sensitive
• BRN: 2414686
• CAS DataBase Reference: (-)-MENTHYL CHLOROFORMATE(CAS DataBase Reference)
• NIST Chemistry Reference: (-)-MENTHYL CHLOROFORMATE(14602-86-9)
• EPA Substance Registry System: (-)-MENTHYL CHLOROFORMATE(14602-86-9)

Safety Data

• Hazard Codes: T,N
• Statements: 23-34-51/53
• Safety Statements: 26-36/37/39-45-61
• RIDADR: UN 3277 6.1/PG 2
• WGK Germany: 3
• F: 10-19-21
• HazardClass: 6.1
• PackingGroup: II
• Hazardous Substances Data: 14602-86-9(Hazardous Substances Data)

Usage

Uses

Used in Organic Chemistry:
(-)-Menthyl Chloroformate is used as a reagent for the asymmetric chlorination of silyl enol ethers. This application is particularly valuable in organic chemistry due to its ability to perform the reaction under mild conditions and produce good yields.
Used in Pharmaceutical Industry:
In the pharmaceutical industry, (-)-menthyl chloroformate may be utilized in the synthesis of various drugs and medicinal compounds. Its ability to facilitate asymmetric chlorination can be beneficial in creating specific drug candidates with desired stereochemistry, which is crucial for their efficacy and safety.
Used in Chemical Research:
(-)-Menthyl chloroformate can also be employed in academic and industrial research settings, where its unique properties can be explored for new applications and reactions. This may lead to the development of novel chemical processes and the creation of new compounds with potential applications in various fields.

InChI:InChI=1/C11H19ClO2/c1-7(2)9-5-4-8(3)6-10(9)14-11(12)13/h7-10H,4-6H2,1-3H3/t8-,9+,10-/m1/s1

Upstream product

• 75-44-5 phosgene 
• 2216-51-5 (-)-menthol 
• 32315-10-9 bis(trichloromethyl) carbonate 
• 503-38-8 trichloromethyl chloroformate 

Downstream Products

• 111612-17-0 5-(-)-menthyloxycarbonyl-(6R)-tetrahydrofolic acid 
• 111482-05-4 5-(-)-menthyloxycarbonyl-(6S)-tetrahydrofolic acid 
• 131177-40-7 1-menthyloxycarbonylpyrrolidine 
• 131119-62-5 1-menthyloxycarbonylpiperidine 
• 153996-48-6 2,3:4,5-di-O-cyclohexylidene-1-O-(1R)-menthyloxycarbonyl-D-myo-inositol 
• 127275-06-3 dimethyl (-)-menthoxycarbonyl-S-malate 
• 139640-08-7 1-O-(-)-menthoxycarbonyl-myo-inositol 
• 139686-86-5 1-O-menthyloxycarbonylmyo-inositol 
• 146564-72-9 (-)-(1'R)-(2',2'-Dimethylspiro<2.4>hepta-4',6'-dien-1-yl)methyl menthyl carbonate 

Relevant articles and documents

A convenient resolution method for 1,1′-bi-2-naphthol and 4,4′-dibromo-1,1′-spirobiindane-7,7′-diol with menthyl chloroformate in the presence of TBAB

A convenient resolution method for 1,1′-bi-2-naphthol and 4,4′-dibromo-1,1′-spirobiindane-7,7′-diol has been developed with crude (-)-menthyl chloroformate as the resolution reagent in the presence of tetrabutylammonium bromide acting as a phase transfer catalyst in an aqueous NaOH/CH2Cl2 two phase solution. The deprotection of the hydroxy group was carried out via an aqueous KOH/EtOH solution. Both enantiomers of 1,1′-bi-2-naphthol and 4,4′-dibromo-1,1′- spirobiindane-7,7′-diol were obtained in high yields. Both ee's of (S)-(+) and (R)-(-)-4,4′-dibromo-1,1′-spirobiindane-7,7′-diol were above 99%. Most of the (-)-menthol could be easily recovered in a deprotection procedure and thus be reused for the formation of (-)-menthyl chloroformate without further purification.

An efficient and practical synthesis of BINAM derivatives by diastereoselective [3,3]-rearrangement

This work describes an efficient, practical, and diastereoselective synthesis of enantiomerically pure BINAM derivatives by utilizing the acid-catalyzed [3,3]-sigmatropic rearrangement of readily accessible N-(-)-menthoxycarbonyl-diaryl hydrazines as a key step. The yield of the rearrangement is very high and two diastereomers thus obtained are easily separable.

Synthesis method of acetaldehyde alcohol optical active ester

The invention provides a synthesis method of an acetaldehyde alcohol optical active ester, which comprises the following steps of: reacting L-menthol as a raw material with triphosgene to obtain L-menthyl chloroformate, reacting the L-menthyl chloroformate with 1, 4-cis-butenediol, recrystallizing, and carrying out oxidation reaction under an ozone condition to obtain the acetaldehyde alcohol optical active ester. In the whole synthesis process, the initial raw materials are low in price and easy to obtain, the synthesis process is simple, the synthesis conditions are mild, and the synthesis cost of the acetaldehyde alcohol optical active ester is greatly reduced. The raw materials are good in reaction selectivity and high in atom utilization rate, and the obtained acetaldehyde alcohol optical active ester has high yield and purity. Meanwhile, few three-waste pollutants are generated in the synthesis process, and the method is suitable for industrial large-scale production of the acetaldehyde alcohol optical active ester, so that large-scale synthesis of drugs such as emtricitabine and lamivudine is facilitated.

Spiro Scaffold Chiral Organocatalyst of 3,2′-Pyrrolidinyl Spiro-oxindole Amine and Its Catalytic Evaluation in the Enantioselective Aldol Condensation between 3-(3-Hydroxy-1 H-pyrazol-1-yl)-Oxindole and Paraformaldehyde

The spiro scaffold chiral organocatalyst of 3,2′-pyrrolidinyl spiro-oxindole amine was successfully prepared from racemic spiro-oxindole amine using l-menthol as a chiral pool in 4 steps in 28%-40% overall yields with at least 99% ee in scale-up preparation, and its catalytic activity was evaluated in the enantioselective aldol condensation between 3-(3-hydroxy-1H-pyrazol-1-yl)-oxindole and paraformaldehyde. The spiro organocatalyst showed superior catalytic activity and selectivity compared with its counterparts, and most substrates offered good to excellent results with up to 96% yield in 96% ee.

PROCESS FOR PRODUCING CHLOROFORMATE COMPOUND

The present invention provides a method for safely producing a large amount of chloroformate compound with high yield. The chloroformate compound can be produced by mixing and reacting a solution of triphosgene, an amine and an alcohol compound in a flow reactor. The chloroformate compound can also be produced by mixing and reacting a solution of triphosgene with a solution comprising an amine and an alcohol compound in a flow reactor. The amine is preferably tributylamine, and preferably used in an amount of 0.8 to 3 equivalents relative to an amount of the alcohol compound.

A preparation method of lamivudine

The invention discloses a method for preparation of lamivudine. Refined pure 5 S - (cytosine base - 1 ') - 1, 3 - oxathiolane - 2 - ethoxy carbonyl - (1' R, 2'S, 3' R) - menthyl ester; in the weak base and the solvent removed under the condition of chiral L - menthol to get a product of lamivudine. The material of the invention is cheap, the reagents used in the environmental protection, steps is relatively short, mild reaction conditions, atom utilization rate high, high yield, high chemical purity of the obtained product, reach the medical standard, suitable for large-scale production of lamivudine preparation method.

A Suitqable to preparation method

The invention discloses a Suitqable to preparation method. Refined pure 5 S - (5 '- fluorocytosine yl - 1') - 1, 3 - oxathiolane - 2 - ethoxy carbonyl - (1 'R, 2'S, 3' R) - menthyl ester; in the weak base and the solvent removed under the condition of chiral L - menthol get products Suitqable to. The invention required the starting raw material is cheap, mild reaction conditions, the atom utilization rate is high, the operation technique is simple, the reagents used in the environmental protection, the resulting high purity, reach the medical standard, is suitable for the industrial production of kindness or gemcitabine.

Safe and Efficient Phosgenation Reactions in a Continuous Flow Reactor

Phosgene is widely used in organic synthesis owing to its high reactivity, utility, and cost efficiency. However, the use of phosgene in batch processes on the industrial scale is challenging owing to its toxicity. An effective method to minimize reaction volumes and mitigate the safety risks associated with hazardous chemicals is the use of flow reactors. Consequently, we have established a flow reaction system using triphosgene and tributylamine, which affords a homogeneous reaction that avoids clogging issues. In addition, we have demonstrated that this methodology can be applied to a wide variety of phosgene reactions, including the preparation of pharmaceutical intermediates, in good to excellent yields.

Levorotatory meptazinol prodrug as well as preparation method and purpose thereof

The invention provides a levorotatory meptazinol prodrug as well as a preparation method and a purpose thereof, wherein the levorotatory meptazinol prodrug is a compound as shown in a formula I or a stereoisomer, a geometrical isomer, a tautomer, oxynitride, a hydrate, a solvate, a metabolite or a pharmaceutically acceptable salt of the compound as shown in the formula I. The compound is low in hepatic first pass effect and high in bioavailability; a medicine which uses the compound as an active component can be used for treating a neurodegenerative disease or various kinds of acute and chronic pain, such as a wound, postoperative, obstetrical and cancer pain, hemicrania, neuropathic pain and the like.

Variochelins, Lipopeptide Siderophores from Variovorax boronicumulans Discovered by Genome Mining

Photoreactive siderophores have a major impact on the growth of planktonic organisms. To date, these molecules have mainly been reported from marine bacteria, although evidence is now accumulating that some terrestrial bacteria also harbor the biosynthetic potential for their production. In this paper, we describe the genomics-driven discovery and characterization of variochelins, lipopeptide siderophores from the bacterium Variovorax boronicumulans, which thrives in soil and freshwater habitats. Variochelins are different from most other lipopeptide siderophores in that their biosynthesis involves a polyketide synthase. We demonstrate that the ferric iron complex of variochelin A possesses photoreactive properties and present the MS-derived structures of two degradation products that emerge upon light exposure.