471-10-3

Usage

InChI:InChI=1/C10H17Cl/c1-5-10(4,11)8-6-7-9(2)3/h5,7H,1,6,8H2,2-4H3

Upstream product

• 4490-10-2 geranyl chloride 
• 123-35-3 7-methyl-3-methene-1,6-octadiene 
• 106-24-1 Geraniol 
• 563-52-0 2-chloro-3-butene 
• 2270-59-9 1-bromo-4-methylpent-3-ene 
• 503-60-6 3,3-dimethyl-allyl chloride 
• 78-79-5 isoprene 
• 67-66-3 chloroform 
• 126-90-9 (S)-(+)-linalool 
• 7719-12-2 phosphorus trichloride 
• 7647-01-0 hydrogenchloride 
• 106-25-2 Nerol 
• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 98-88-4 benzoyl chloride 

Downstream Products

• 115-95-7 linalool acetate 
• 126-91-0 linalool 
• 78-70-6 3,7-dimethylocta-1,6-dien-3-ol 
• 18172-67-3 beta-pinene 
• 5392-40-5 (E/Z)-3,7-dimethyl-2,6-octadienal 

Relevant academic research and scientific papers

Formamide-Catalyzed Nucleophilic Substitutions: Mechanistic Insight and Rationalization of Catalytic Activity

Herein, detailed mechanistic investigations into formamide-catalyzed nucleophilic substitution (SN) of alcohols are reported. Alkoxyiminium chlorides and hexafluorophosphates were synthesized and characterized as a key intermediate of the catalytic cycle. The determination of reaction orders and control experiments indicated that the nucleophilic attack of the formamide catalyst onto the reagent BzCl is the rate-determining step. Linear free energy relationship revealed a correlation between the quantified Lewis basicity strength of formamides by means of 11B NMR spectroscopy and their catalytic activity in SN-transformations. The observed difference in catalytic ability was attributed to the natural bond order charge, dipole moment, and Sterimol parameter B5. Importantly, this rationalization enables the prediction of the capacity of formamides to promote SN-type transformations in general.

Nucleophilic Substitutions of Alcohols in High Levels of Catalytic Efficiency

A practical method for the nucleophilic substitution (SN) of alcohols furnishing alkyl chlorides, bromides, and iodides under stereochemical inversion in high catalytic efficacy is introduced. The fusion of diethylcyclopropenone as a simple Lewis base organocatalyst and benzoyl chloride as a reagent allows notable turnover numbers up to 100. Moreover, the use of plain acetyl chloride as a stoichiometric promotor in an invertive SN-type transformation is demonstrated for the first time. The operationally straightforward protocol exhibits high levels of stereoselectivity and scalability and tolerates a variety of functional groups.

Systematic Evaluation of Sulfoxides as Catalysts in Nucleophilic Substitutions of Alcohols

Herein, a method for the nucleophilic substitution (SN) of benzyl alcohols yielding chloro alkanes is introduced that relies on aromatic sulfoxides as Lewis base catalysts (down to 1.5 mol-%) and benzoyl chloride (BzCl) as reagent. A systematic screening of various sulfoxides and other sulfinyl containing Lewis bases afforded (2-methoxyphenyl)methyl sulfoxide as optimal catalyst. In contrast to reported formamide catalysts, sulfoxides also enable the application of plain acetyl chloride (AcCl) as reagent. In addition, it was demonstrated that weakly electrophilic carboxylic acid chlorides like BzCl promote Pummerer rearrangement of sulfoxides already at room temperature. This side-reaction also provided the explanation, why sulfoxide catalyzed SN-reactions of alcohols do not allow the effective production of aliphatic and electron deficient chloro alkanes. Comparison experiments provided further insight into the reaction mechanism.

A General Catalytic Method for Highly Cost- and Atom-Efficient Nucleophilic Substitutions

A general formamide-catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol %) of inexpensive trichlorotriazine (TCT), is introduced. This is the first example of a TCT-mediated dihydroxychlorination of an OH-containing substrate (e.g., alcohols and carboxylic acids) in which all three chlorine atoms of TCT are transferred to the starting material. The consequently enhanced atom economy facilitates a significantly improved waste balance (E-factors down to 4), cost efficiency, and scalability (>50 g). Furthermore, the current procedure is distinguished by high levels of functional-group compatibility and stereoselectivity, as only weakly acidic cyanuric acid is released as exclusive byproduct. Finally, a one-pot protocol for the preparation of amines, azides, ethers, and sulfides enabled the synthesis of the drug rivastigmine with twofold SN2 inversion, which demonstrates the high practical value of the presented method.

Formamides as Lewis Base Catalysts in SNReactions—Efficient Transformation of Alcohols into Chlorides, Amines, and Ethers

A simple formamide catalyst facilitates the efficient transformation of alcohols into alkyl chlorides with benzoyl chloride as the sole reagent. These nucleophilic substitutions proceed through iminium-activated alcohols as intermediates. The novel method, which can be even performed under solvent-free conditions, is distinguished by an excellent functional group tolerance, scalability (>100 g) and waste-balance (E-factor down to 2). Chiral substrates are converted with excellent levels of stereochemical inversion (99 %→≥95 % ee). In a practical one-pot procedure, the primary formed chlorides can be further transformed into amines, azides, ethers, sulfides, and nitriles. The value of the method was demonstrated in straightforward syntheses of the drugs rac-Clopidogrel and S-Fendiline.

METHOD OF CONVERTING ALCOHOL TO HALIDE

The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.

Allylic and allenic halide synthesis via NbCl5- and NbBr 5-mediated alkoxide rearrangements

(Chemical Equation Presented) Addition of NbCl5 or NbBr 5 to a series of magnesium, lithium, or potassium allylic or propargylic alkoxides directly provides allylic or allenic halides. Halogenation formally occurs through a metallahalo-[3,3] rearrangement, although concerted, ionic, and direct displacement mechanisms appear to operate competitively. Transposition of the olefin is equally effective for allylic alkoxides prepared by nucleophilic addition, deprotonation, or reduction. Experimentally, the niobium pentahalide halogenations are rapid, afford essentially pure (E)-allylic or -allenic halides after extraction, and are applicable to a range of aliphatic and aromatic alcohols, aldehydes, and ketones. 2009 American Chemical Society.

Semiempirical AM1 Calculations on the Competing 1- and 4-Alkylation of 2-Methylbuta-1,3-diene with Primary Allylic Cations

The strict regioselectivity of the attack of various carbenium ions on 2-methylbuta-1,3-diene at C-1 is not valid in the case of primary-tertiary allylic cations (such as 2-5) which also attack at C-4 (≈20%), a phenomenon which is rationalized by a cyclic HOMO-LUMO interaction of isoprene and allylic cations.

Reactions of α-haloallyllithium derivatives with carbon, silicon, tin or boron halides and carbonyl compounds

A series of allylic halides have been converted into their α-carbanions with strong lithium bases, using different techniques.These have been compared in their reaction with various electrophiles leading to functionally substituted allyl derivatives.The influence of the counterion on the regio- and stereoselectivity has been investigated. allylic halides / α-halocarbanions / allylsilanes / allyltin derivatives / α-chlorohydrins / vinylepoxides / diastereoselectivity

Rearrangement of Linalool, Geraniol, and Nerol and Their Derivatives

Acid-catalyzed conversion of linalool into geraniol, nerol, and α-terpineol is slower than the corresponding reactions of geraniol and nerol, because the tertriary linalyl carbocation reverts to linalool rather than going forward to rearranged products.The linalyl carbocation does not lose its stereochemical identity, and oxygen exchange of linalool is faster than rearrangement or cyclization.Solvolyses of linalyl esters and chloride are faster than those of the geranyl and neryl derivatives.These solvolyses are different from acid heterolysis of linalool in that there is extensive racemization of linalool, but cyclization to α-terpineol goes with considerable retention of configuration.Participation by the 6,7-double bond controls the stereochemistry of linalool heterolysis and solvolysis of linalyl esters, but it does not markedly affect the reaction rates.