Chloroallylation

With mercuric salt catalysts, hydrogen chloride adds to give 2-chloroallyl alcohol, 2-chloroprop-2-en-l-ol [5976-47-6] (27). 

The acid promoted cyclization of AT-(2-chloroallyl)enaminones (Scheme 35a) provides the expected 3-methyltetrahydroindoles, whereas similar treatment of iV-(2-chloroallyl)anilines yields unexpectedly 2-, rather than 3-, methylindoles (Scheme 35b) (75JCS(Pl)U46). The course of the latter cyclization is not resolved although various intermediates, such as those shown, have been considered. The ring closure in the furan synthesis shown in Scheme 35c is catalyzed by mercury(II) ion (79JCs(Pl)316l). 

Formaldthyde Arylsulfonamide resin, chloroallyl-hexaminium chloride... 

Starnes et al.hl have also suggested that the head adduct may undergo p-scission to eliminate a chlorine atom which in turn adds VC to initiate a new polymer chain. Kinetic data suggest that the chlorine atom does not have discrete existence. This addition-elimination process is proposed to he the principal mechanism for transfer to monomer during VC polymerization and it accounts for the reaction being much more important than in other polymerizations. The reaction gives rise to terminal chloroallyl and 1,2-dichlorocthyl groups as shown in Scheme 4.8. 

Maddy KT, Fong HR, Lowe JA, et al. 1982. A study of well water in selected California communities for residues of 1,3-dichloropropene, chloroallyl alcohol and 49 organophosphate or chlorinated hydrocarbon pesticides. Bull Environ Contam Toxicol 29 354-359. 

Oda et al. reported that under reflux conditions, the zinc-promoted reaction of 2,3-dichloro-l-propene with aldehydes and ketones in a two-phase system of water and toluene containing a small amount of acetic acid gave 2-chloroallylation products (Eq. 8.31).64 No conversion occurred when tin was used as the promoter. The absence of water completely shuts down the reaction. Interestingly, the action of 2,3-dichloropropene plus zinc powder in aqueous ethanol gives the dechlorination product, allene.65... 

Cationic surfactants contain a positively charged headgroup and are typically used as conditioners to improve hair manageability and reduce static. Cationic surfactants are especially irritating to eyes when used in high concentrations but are safe and useful in low amounts. Quatemium-15 (chloroallyl methanamine chloride, Fig. 7.9.4) is a cationic surfactant included in shampoo formulations... 

Figure 7.9.4 The cationic surfactant quatemium-15 (chloroallyl methanamine chloride).

In an anionic approach, the sodium salt of the chiral chloroallyl phosphonamide 132 engages in nucleophilic addition onto oximes and gives the optically pure A-alkoxy aziridines... 

Negishi first observed the insertion of the y-halolithium species 75 obtained by deprotonation of propargyl chloride into octylzirconocene chloride protonation of the product afforded the allene 79 (Scheme 3.20) [37]. The overall effect is insertion of an allenyl carbenoid. The a-halolithium equivalent 76 is conveniently generated by addition of two equivalents of base to 2-chloroallyl chloride [52] and affords the same products. The organome-tallic product 77 of allenyl carbenoid insertion is either in equilibrium with the propargyl... 

An alternative and more efficient preparation is achieved in the case of 1-allenyl-benzotriazole (250), which proceeds by dehydrochlorination of l-(2-chloroallyl)ben-zotriazole (251) by NaOH in dimethyl sulfoxide under reflux (Eq. 8.36) [147]. 

Dichlorination of tetramethylallene afforded 3-chloro-2,4-dimethyl-l,3-pentadiene as the single product, whereas the same reaction of 1,1-dimethylallene yielded a mixture of 2-chloro-3-methyl-l,3-butadiene, 2,3-dichloro-3-methyl-l-butene and 1,2-dichloro-3-methyl-2-butene, indicating the intermediacy of the 2-chloroallylic cationic intermediate 11 [13]. 

Even the reaction with 1,1-disubstituted allenes delivered 2-chloroallyl alcohols 16 with the hydroxyl group connected to the more substituted terminus [15]. 

The chlorine atom adds in the gas phase to propadiene (la) with a rate constant that is close to the gas-kinetic limit. According to the data from laser flash photolysis experiments, this step furnishes exclusively the 2-chloroallyl radical (2a) [16, 36], A computational analysis of this reaction indicates that the chlorine atom encounters no detectable energy barrier as it adds either to Ca or to Cp in diene la to furnish chlorinated radical 2a or 3a. A comparison between experimental and computed heats of formation points to a significant thermochemical preference for 2-chloroal-lyl radical formation in this reaction (Scheme 11.2). Due to the exothermicity of both addition steps, intermediates 2a and 3a are formed with considerable excess energy, thus allowing isomerizations of the primary adducts to follow. 

In the first step, Ag+ promotes the departure of Cl- to give a cyclopropyl carbocation. This undergoes two-electron disrotatory electrocyclic ring opening to give the chloroallylic cation, in which the empty orbital is localized on Cl and C3. Then 09 can add to C3 desilylation then gives the product. 

Soil Hydrolyzes in wet soil forming a5-3-chloroallyl alcohol (Castro and Belser, 1966). 

Synonyms BRN 1719558 /7 a/ 5-3-Chloroallyl chloride ( )-l,3-Dichloropropene lra/ 5-l,3-Di-chloropropene ( )-l,3-Dichloro-l-propene rra/ 5-l,3-Dichloro-l-propene 1,3-Dichlororoprop-l-ene /ra/ 5-l,3-Dichloro-l-propylene NSC 6202 EPA pesticide chemical code 029001 RCRA waste number U084 ra/ s-Telone Telone 2000 Telone C Telone C 17 Telone 11 UN 2047. 

Chloroacetophenone, see a-Chloroacetophenone Q-Chloroacetophenone, see a-Chloroacetophenone cfs-3-Chloroallyl chloride, see cfs-l,2-Dichloropropylene frarrs-3-Chloroallyl chloride, see frarrs-l,2-Dichloro-... 

In polar aprotic solvents (DMF, DMSO) above 180°C, (2-chloroallyl-thio)- (63) and propargylthiotropones (64) undergo thio-Claisen rearrangements and form thienotropone 65 in good yields [Scheme 17 83H(20)1709]. 

Pentazocine has been successfully used to relieve labour pain [201] and its obstetric use in place of pethidine is favoured by,its apparent inferior ability to pass the placental barrier [206]. A clinical trial of (+)- and (-)-pentazocine adds to the rare number of examples in which optical enantiomorphs have been evaluated [207]. In post-operative patients, response to 60 mg of the dextro isomer was less than that to 5 mg of morphine, while 25—29 mg of (-)-pentazocine was as effective as 10 mg of morphine. Hence most of the activity of the race-mate resides in the laevo isomer, as anticipated from results in animals [208]. Several studies of the distribution, excretion and metabolism of pentazocine have been made. Peak levels of the tritium-labelled drug (and its c/s-3-chloroallyl analogue) were present in the C.N.S. of a cat within 40 minutes of intramuscular administration [209], the comparable figure for morphine being 2 hours [210]. 

Synonyms 1,3-DCP a-chloroallyl chloride 1,3-dichloropropylene Telone Telone II DD fumigants... 

Toxicological Significance of Oxidation and Rearrangement Reactions of iS -Chloroallyl Thio-and Dithiocarbamate Herbicides... 

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