Farm. Nueva (Madrid) published new progress about 4584-49-0. 4584-49-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Salt,Amine,Aliphatic hydrocarbon chain, name is 2-Chloro-N,N-dimethylpropan-1-amine hydrochloride, and the molecular formula is C5H13Cl2N, COA of Formula: C5H13Cl2N.
Marquina, J. G. published the artcileDerivatives of N-methyl-4-phenylpiperidine-4-carboxylic acid and 2,2-diphenyl-4-dimethylaminovaleric acid, COA of Formula: C5H13Cl2N, the publication is Farm. Nueva (Madrid) (1961), 381-92, database is CAplus.
Methylbis(2-hydroxyethyl)amine (75 g.) in 75 ml. anhydrous C6H6 was added slowly with stirring to 125 mi. SOCl2 in 75 ml. C6H6 below 50° the mixture heated 2 hrs. at 50-5°, SOCl2 removed in vacuo on a water bath, alc. added, the solution concentrated, and the solid crystallized from 500 ml. Me2CO to give 72 g. methylbis(2-chloroethyl)amine-HCl (I), m. 110°; picrate, m. 133°. To 70.2 g. PhCH2CN and 115.2 g. I in 400 ml. C6H6 at 30-40° was added slowly with stirring 100 g. NaNH2, the mixture refluxed 2 hrs., diluted with H2O and extracted with HCl, the solution made alk. and extracted with Et2O, and the extract distilled in vacuo to give 63 g. N-methyl-4-phenylpiperidine-4-nitrile (II), b4 148°, m. 53°; HCl salt m. 221-2°. A mixture of 478 g. II, 637 g. H2SO4, and 155 ml. H2O was heated 1 hr. at 145-50°, cooled and treated with NH3 to pH 7-8 and the solid filtered off and washed to give 330 g. N-methyl-4-phenylpiperidine-4-carboxylic acid (III), m. 301-2° (H2O). To 27 g. III was added slowly 40 ml. SOCl2, the mixture heated 1 hr. on a water bath, 100 ml. C6H6 was added, the mixture allowed to crystallize, the solution filtered, and the solid washed with C6HO and petr. ether to give 27.5 g. III acid chloride (IV), which was used immediately. NaCN (25 g.) in 90 ml. H2O was added slowly with stirring to 100 ml. H2O containing 100 g. BzH bisulfate. the solution extracted with C6H6, the dry extract added slowly with stirring to 200 ml. C6H6 containing 135 g. AlCl3 at 8 10° and the mixture kept 1 day then heated 1 hr. at 80° washed with H2O and distilled in vacuo to give 67 g. diphenylacetonitrile (V), b1-2 122-5°, m. 69-70°. SOCl2 (67 g.) in 100 ml. C6H6 was added to 50 g. 1-dimethylamino-2-propanol in 100 ml. C6H6 at 20-5°, the solution refluxed 2 hrs., cooled, and the mixture filtered, and the solid recrystallized to give 60 g. 2-chloro-1-dimethylaminopropane-HCl (VI.HCl), m. 185-6°. To 72 g. V and 55 g. pulverized NaOH was added 90 g. VI in Et2O, the EtO distilled, the mixture heated to 95-100° with stirring for 10 hrs., washed with H2O, treated with anhydrous HCl, rehydrolyzed, and distilled in vacuo to give 45 g. 2,2-diphenyl-4-dimethylaminovaleronitrile (VII), b1-2 180-4°, m. 91° (petr. ether). To 600 g. VII was added 650 ml. H2SO4 in 420 ml. H2O, the solution heated 5 hrs. at 150°, cooled and filtered to give 570 g. 2,2-diphenyl-4-dimethylaminovaleric acid-H2SO4 (VIII.H2SO4), m. 224-6° (H2O). To 40 g. VIII was added 40 ml. SOCl2, and the mixture refluxed 1 hr. on a steam bath, treated with 100 mi. C6H6, cooled, allowed to crystallize, filtered, and washed with C6H6-petr. ether to give 41.5 g. VIII acid chloride (IX) which was used immediately. Et carbamate (17.8 g.) in 250 ml. C6H6 was added with stirring to 10 g. 50% NaH in mineral oil in 150 ml. C6H6 at 6-7°, and the mixture stirred 30 min., treated slowly with 24.7 g. III in 150 ml. C6H6 at 6-7°, stirred 2 hrs., then 4 hrs. at ambient temperature, extracted with 5% HCl, treated with Na2CO3, extracted with C6H6, and distilled in vacuo to give 7 g. N-methyl-4-phenylpiperidine-4-carboxyethyl carbamate (X), m. 140-1.5 (Me2CO). Similarly, the following esters of III were prepared (alkyl carbamate and m.p. given): Pr, 138-9.5°; iso-Pr, 136-8°; allyl, 112-13.5°; Bu, 99.5-100.5° (picrate m. 163-4.5°; HCl salt m. 108-10°). Et carbamate (26.7 g.) in 300 ml. C6H6 was added with stirring to 6.9 g. finely divided Na in 150 ml. C6H6 at 6-7% and the mixture stirred 30 min., treated slowly at 6-7° with 41.4 g. IX suspended in 150 ml. C6H6, stirred 2 hrs. at 6-7° then 4 hrs. at ambient temperature, washed with H2O, extracted with 5% HCl, and treated with Na2CO3 to give 10 g. Me2NCHMe CH2CPh2CONHCO2Et, m. 153-4.5° (Me2CO). Similarly were prepared the following esters of VIII (alkyl carbamate, m.p. given): Pr, 158-9°; iso-Pr, 140-1°; allyl, 139-9.5°; Bu, 97-7.5° picrate, m. ∼128°. Analgesic activity was nil for derivatives of VI and VIII. Spasmolytic activity was slight for derivatives of VI, but high for derivatives of VIII.
Farm. Nueva (Madrid) published new progress about 4584-49-0. 4584-49-0 belongs to chlorides-buliding-blocks, auxiliary class Chloride,Salt,Amine,Aliphatic hydrocarbon chain, name is 2-Chloro-N,N-dimethylpropan-1-amine hydrochloride, and the molecular formula is C5H13Cl2N, COA of Formula: C5H13Cl2N.
Referemce:
https://en.wikipedia.org/wiki/Chloride,
Chlorides – an overview | ScienceDirect Topics