7-Bromopropyl chloride

SYNS 3-BROMOPROPYL CHLORIDE 1,3-CHBP (0-CHLOROBROMOPROPANE l-CHLORO-3-BROMOPROPANE pOT) 3-CHLOROPROPYL BROMIDE TRIMETHYLENE BROMIDE CHLORIDE TRIMETHYLENE CHLOROBROMIDE... 

BROMOPROPIONIC ACID see BOB250 P-BROMOPROPIONIC ACID see BOB250 3-BROMOPROPYL CHLORIDE see BNA825 3-BROMOPROPYLENE see AFYOOO 3-BROMO-l-PROPYNE see PMN500... 

BROMOPROPYL CHLORIDE (109-70-6) May react with aluminum powder, liquid oxygen, potassium, sodium. Elevated temperatures or contact with hot surfaces produce hydrogen bromide and hydrogen chloride. 

The second route involves the palladium catalyzed coupling of iodoaniline 51 with the acyl silane 54 in the presence of DABCO to give the 2-trimethylsilyl indole 55. The acyl silane 54 was prepared by alkylation of 1,3-dithianyl-trimethylsilane with (3-bromopropyl)-dimethylamine to give 56, followed by removal of the dithioacetal with mercuric oxide and mercuric chloride. Finally, desilylation of 55 in aqueous HCl and methanol afforded rizatriptan (4). 

The present procedure is that of Ing and Manske1 and avoids the troublesome preparation of potassium phthalimide. Diphthalimide-propane and a-bromopropyl phthalimide are conveniently prepared by the same general procedure. In a similar manner, /3-phenylethyl bromide gives a 76 per cent yield of /3-phenylethyl phthalimide while only a very small amount of styrene is formed in the reaction. The only other feasible preparative method for benzyl phthalimide is from benzyl chloride and potassium phthalimide.2... 

Alkylation of the sulfur atom of thietane with allyl bromides (or chlorides) gives allyl 3-bromopropyl sulfides, useful intermediates in the synthesis of larger rings, as illustrated by the conversion of thietane to 2-vinylthiolane. ... 

Hanford and Adams stated that cyclization of 2-(3-bromopropyl)dihy-droquinazoline (266) by means of alkali afforded only the linear isomer 124. Compound 266 was prepared from 2-nitrobenzylamine and phenoxybu-tyryl chloride, as shown below ... 

Tosyl chloride added to a stirred soln. of p-nitraniline in pyridine, and heated 30 min. on a steam bath under anhydrous conditions N-(p-nitrophenyl)-p-toluenesulfonamide (Y 95%) dissolved in dimethyl sulfoxide, treated with K-carbonate and 1,3-dibromopropane, stirred 5 days at room temp. N-(3-bromopropyl)-N-(p-nitrophenyl)-p-toluenesulfonamide (Y 80%) added to a mixture of ethyl acetoacetate, a 53.5%-dispersion of NaH in mineral oil, and ferf-butanol (previously warmed with stirring under anhydrous conditions until the NaH has dissolved and Hg-evolution ceased), refluxed 20 hrs. with stirring, and the resulting crude ethyl 2-acetyl-5-p-nitranilino)-N-(p-toluenesulfonyl)-valerate refluxed 48 hrs. with guanidine carbonate in ferf-butanol 2-amino-6-methyl-5- [ (N-p-toluenesulfonyl-p-nitranilino) propyl] -4-pyrimidinoI (Y 69%). F. e. s. B. R. Baker, D. V. Santi, and H. S. Shapiro, J. Pharm. Sci. 53, 1317 (1964). 

The B-ferf-butyl-9-BBN can also be obtained from B-isopropyl-9-BBN. The B-isopropyl-9-BBN on bromination in methylene chloride with continuous removal of HBr gives B-2 -bromopropyl-9-BBN. The bromoderivative on treatment with methyllithium provides B-tert-butyl-9-BBN (Chart 23.5) [3], in quantitative yield. 

The first application of the alkyltrifluoroborate salts was the conversion into alkyldihaloboranes by silyl hahdes and subsequent reaction with alkyl azides [77]. An example of a usefid synthesis was the preparation of (S)-2-phenylpyrrolidine (141) (Scheme 8.32). (S)-DICHED (3-bromopropyl)boronate (13S) was converted into the 3-azido derivative 136 at reflux temperature under phase-transfer conditions. The usual reaction with (dichloromethyl)lithium followed by phenylmagnesium bromide to form DICHED ester 137 was followed by treatment with potassium bifluoride in aqueous methanol to provide the alkyltrifluoroborate salt 138. Neither boronic esters nor alkyltrifluoroborate salts react with alkyl azides. Reaction of 138 with trimethylsi-lyl chloride yielded (S)-2-phenylpyrrolidine (141), but reaction with silicon tetrachloride proved much faster and more efficient. At first it was thought that the intermediates 139 and 140 were probably difluoroboranes in accord with literature precedent [76], but careftil reinvestigation has revealed that reaction of alkyltrifluoroborate salts with silicon tetrachloride in coordinating solvents yields alkyldichloroboranes [78]. 

Lanthanide bis(trifluoromethylsulfonyl)amides Ln[N(S02CF3)2] catalyse the acetylation of anisole by acetic anhydride in good yield with easy catalyst recovery. The Friedel-Crafts acetylation of (3-bromopropyl)benzene by acetyl chloride to form p-(3-bromopropyl)acetophenone together with a little of the 3-chloro analogue has been studied. The acylation of phenol by acetic acid has been subject to... 

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