Patent GB-761001-A (GB)
Title: Halogenated tertiary mono and di-amine-n-oxides and a process for preparing the same
IPC: C07C291/04
Filed: 1954-06-18
Abstract: The invention comprises a halogenated tertiary mono- or di-amine-N-oxide of the formula <FORM:0761001/IV(b)/1> wherein R1 and R2 are the same or different alkyl, alkenyl, haloalkyl, aryl, aralkyl, cycloalkyl, alkoxyalkyl, cyanoalkyl, carbamoylalkyl, carboxyalkyl or carbalkoxyalkyl groups, or a radical of the formula <FORM:0761001/IV(b)/2> wherein X1, X2 and X3 are hydrogen or halogen and the compound contains at least one halogen; wherein n1, n2, n3 and n4 are each integers, and wherefrom the N-oxides of bis-(chloroethyl)-methyl (or ethyl)-amine, tris-(chloroethylamine) and dibenzyl (or diethyl)-chlorethylamine are excluded.  Such compounds are obtained by the oxidation with inorganic or organic peroxides of the corresponding amine derivatives.  Reference is also made to electrolytic oxidation.  Oxidizing agents specified are hydrogen peroxide, ozone, organic or inorganic peracids, reagents which produce peracids, peroxides and ozonides, e.g. performic, peracetic, perbenzoic and perphthalic acids, and salts of perboric and periodic acids, and peroxides of ether, alkali metals and alkaline earth metals.  Peracids may be produced in the reaction mixture, e.g. the anhydride of formic, acetic, propionic, butyric, succinic or glutaric acid is reacted with hydrogen peroxide in the presence or absence of a dehydrating agent, or the addition products of aldehydes and ketones with hydrogen peroxide, ozonides and electrolytic oxidation may be used.  A pH of 2 to 9 and a temperature of 5 DEG  to 40 DEG  C. are suitable reaction conditions.  The products may be separated as salts with hydrochloric, sulphuric, nitric, perchloric, picric, picrylsulphonic, flavianic, 5-naphthalene-disulphonic and camphor-a -chloro-p -sulphonic acid. In example (1) N,N1 - tetrakis - (b  - chloroethyl)-trimethylene diamine is reacted at below 30 DEG  C. with peracetic acid.  The product N,N1-tetrakis - (b  - chloroethyl) - trimethylene diamine-N,N1-dioxide is isolated as its picrate which is then converted to the hydrochloride.  In a generally similar manner, there are prepared (2) benzyl-bis-(b -chloroethyl)-amine-N-oxide; (3) isoamyl-bis-(b -chloroethyl)-amine-N-oxide; (4) cyclohexyl-bis-(b -chloroethyl)-amine - N - oxide; (5) diethylaminoethyl-bis-(b  - chloroethyl) - amine - N,N1 - dioxide; (6) methyl - bis - (b  - bromoethyl) - amine - N-oxide; (7) allyl - bis - (b  - chloroethyl) - amine-N - oxide; (8) n - butyl - bis - (b  - chloroethyl)-amine-N-oxide; (9) and (10) b -ethoxyethyl-bis-(b -chloroethyl)-amine oxide; (11) N-bis-(b -chloroethyl)-glycine ethyl ester N-oxide; (12) N - bis - (b  - chloroethyl) - glycinenitrile-N-oxide; (13) N-bis-(b -chloroethyl)-glycine-amide - N - oxide; (14) N - bis - (b  - chloroethyl)-glycine - N - oxide; (15) N - bis - (b  - chloroethyl) - alanine - N - oxide.  The oxidizing agents used are (2) and (3) perbenzoic acid; (4) to (8) and (10) to (15) peracetic acid, prepared by mixing hydrogen peroxide and acetic acid; and (9) perpropionic acid, prepared by mixing hydrogen peroxide and propionic anhydride.