2-chloroethyl Amine Hydrochloride Research Articles

Complexation properties and synthesis of a novel Schiff base with triphenylene nucleus

We presented the synthesis of a novel Schiff base and its complexation properties with some transition metal ions in this work. For this, the 2,3,4,6,7,10,11 hexahydroxytriphenylene (HHTP) as starting material was synthesized according to known procedure. Moreover, the 2-((2-chloroethylimino)methyl) phenol material was prepared with reaction of salicylaldehyde and 2-chloroethylamine hydrochloride. To give the 2,3,4,6,7,10,11-hexakis(salicyliminoethoxy)triphenylene (HSE-TP) as a novel Schiff base, the HHTP were treated with 2-((2-chloroethylimino)methyl)phenol in acetone media. Complexation properties of this Schiff base were investigated towards Ni(II), Cu(II), Co(II), Zn(II), Pd(II) and Cd(II) as transition metals. The structures of these new compounds (ligand and complexes) were characterized with FT-IR, magnetic susceptibility measurement, thermal methods (TGA), 1H NMR and elemental analyses.

ChemInform Abstract: Synthesis of Some Nitrogen Mustards.

Nitrogen mustards with pyrimidine moiety have been synthesized by condensation of benzaldehyde mustard 7 with 4-hydroxy-2, 6-dimethyl pyrimidine, 4-chloro-2, 6-dimethyl pyrimidine. Also, N, N-bis(2-chloroethyl)amine hydrochloride, ethanolamine and diethanolamine have been condensed with 4-chloro-2, 6-dimethyl-pyrimidine respectively.

Green Synthesis of a Novel Functionalized Tetrahydro-1,4-thiazepine and Computational Studies of Its Tautomeric Structures

Reaction of ethyl-2-cyano-3,3-dimercaptoacrylate dipotassium salt with 2-chloroethylamine hydrochloride in water afforded the novel (4E,6E)-ethyl 5-amino-2,3-dihydro-7-mercapto-1,4-thiazepine-6-carboxylate. The molecular geometry of the most stable tautomeric structure was investigated with DFT and AIM at the B3LYP level of theory using the 6-31G** and 6-311+G** basis sets.

Pyrolytic formation and photoluminescence properties of a new layered carbonaceous material with graphite oxide-mimicking characteristics

Thermal carbonization of bis(2-chloroethyl)amine hydrochloride at 260 °C in air leads to a new, functional layered carbonaceous material that, although different in structure and composition, shares similar characteristics as the well-known graphite oxide. Specifically, the molecularly derived carbonaceous solid is layered with relatively small lateral dimensions, highly dispersible in water providing clear colloidal sols and possesses ion-exchange properties. The carbonaceous solid strongly fluoresces in the visible, when stimulated with a wide range of excitation wavelengths. Overall, the method presents an alternative synthesis towards molecularly derived layered carbonaceous materials with novel properties.

Practical Synthesis of 1-(7-Fluoro-naphthalen-1-yl)piperazine Hydrochloride

A practical and scalable preparation of 1-(7-fluoronaphthalen-1-yl)-piperazine hydrochloride (1) is reported. The original route for the synthesis of this compound involved the use of 1-amino-7-fluoronaphthalene and bis(2-chloroethyl)amine hydrochloride, two highly toxic compounds. A new protocol has been developed that employs a palladium-catalyzed Buchwald–Hartwig cross-coupling reaction between 1-Boc-piperazine and 1-bromo-7-fluoronaphthalene followed by piperazine deprotection with HCl gas. In addition, an efficient palladium removal protocol allowed for the preparation of the target molecule with less than 20 ppm of this metal. This methodology has been successfully implemented to produce multigram quantities of 1 with excellent purity and low palladium content.

Synthesis of a functionalized tetrahydro-1,4-thiazepine in water as the solvent and theoretical investigation of its tautomeric structures

Reaction of sodium 2,2-dicyanoethene-1,1-bis(thiolate) with 2-chloroethylamine hydrochloride in water afforded the novel (Z)-5-amino-7-thioxo-2,3,4,7-tetrahydro-1,4-thiazepine-6-carbonitrile. The molecular geometry of the most stable tautomeric structure was investigated with DFT and AIM at the B3LYP level of theory using the standard 6-31G** basis set.

Preparation of poly(glycidyl methacrylate) grafted sulfonamide based polystyrene resin with tertiary amine for the removal of dye from water

Poly(glycidyl methacrylate) was grafted onto crosslinked poly(styrene) beads through the 2-chloroethyl sulphonamide (CSA) groups present in the resin using ATRP polymerization method. A beaded polymer with a poly(glycidyl methacrylate) surface shell was prepared in three steps, starting from poly(styrene-DVB) (10% crosslinking) based beads with a particle size of 420–590 μm, according to the synthetic protocol; chlorosulfonation, sulfamidation with 2-chloroethylamine hydrochloride and grafting reaction of poly(glycidyl methacrylate). The polymeric resin was prepared with 147.8% of grafted glycidyl methacrylate and subsequent modified with diethyl amine to introduce tertiary amine groups. This resin has also been demonstrated to be an efficient dye sorbent, able to remove dye from water even at ppm levels. The dye sorption capacity under non-buffered conditions is around 0.90 g dye/g resin.

Three-component condensation of pyridin-2-one, bis(2-chloroethyl)amine hydrochloride, and K2CO3 in DMF as a new method for oxazolidinylethylation

Three-component condensation of pyridin-2-one, bis(2-chloroethyl)amine hydrochloride, and K2CO3 in DMF unexpectedly gave N-and O-oxazolidinylethylation products of pyridin-2-one in the ratio 3: 2.

Combined application of 2D NMR correlation methods and ab initio chemical shift calculations to the structure determination of new heterocyclic compounds

The combined use of 2D NMR correlation methods and ab initio chemical shift calculations is efficient and, in some cases, virtually the only way to determine the structures of new organic compounds. This approach enabled us to establish the structure of the major unusual product of the three-component reaction of imidazo[1,5-a]quinoxalin-4-one, bis(2-chloroethyl)amine hydrochloride, and potassium carbonate in DMF.

Synthesis and characterization of water-soluble chitosan derivate and its antibacterial activity

Ethylamine hydroxyethyl chitosan (EHCs) was synthesized from chitosan and chloroethylamine hydrochloride under alkali condition by the novel method described in this study. The effect of several factors, such as reaction time, temperature and the molar ratio of hydroxyethylic chitosan (HECs) to chloroethylamine hydrochloride were discussed. The structure changes of derivative were investigated by FTIR, 13C NMR, DSC and TGA analysis. Good water solubility of EHCs was observed in a wide range of molecular weights. Antibacterial activities of derivative against Escherichia coli ( E. coli) was explored by the optical density method.

A general and convenient synthesis of N-aryl piperazines

A general and convenient synthesis of N-aryl piperazines from bis(2-chloroethyl)amine hydrochloride and a broad range of anilines in diethylene glycol monomethyl ether is described.

Hyperbranch-polyethyleniminated functional polymers. I. Synthesis, characterization of novel ABA type of dumbbell-like polyethyleniminated polyoxypropylenediamines, and their complexing properties with copper(II) ions in aqueous solution

Novel ABA-type dumbbell-like water-soluble copolymers [D230(EI)4, D400(EI)4, and D400(EI)8] were synthesized by introducing ethylenimine (EI) groups into both sides of polyoxypropylenediamines via a simple in situ ethylamination of polyoxypropylenediamine with 2-chloroethylamine hydrochloride. The structures of the resultant polymers were identified by Fourier transform infrared spectroscopy and 1H NMR. The percentages of primary, secondary, and tertiary amine present were determined by the potentiometric titration method after treatments with the appropriate chemicals of salicylaldehyde and acetic anhydride. The surface tension and solubilizing behavior of pyrene in the presence of these polymers in aqueous medium were also investigated, and the efficiency to reduce the surface tension and solubilizing behavior of pyrene depends on the attachments of EI to polymer backbone. The chelating properties of these polymers were examined quantitatively by ultraviolet–visible (UV–vis) spectroscopy in the presence of Cu2+ ions in aqueous solution, and continuous variation analysis revealed that the most stable complex is formed at the normality ratio of [N]/[Cu2+] = 3.0. UV–vis spectroscopy and transmission electron microscopy were used to evaluate the dumbbell-like water-soluble copolymer, D400(EI)8, as a stabilizer for preparing colloidal noble metal nanoparticles (Au and Pt) in aqueous solution. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1360–1370, 2003

The Synthesis of anN,N′-Diformylated 36-Membered N8O4 Oxaazamacrocycle

N-formylation of a secondary aliphatic amine has been achieved through the in situ reaction of potassium o-nitrophenolate, generated from o-nitrophenol, K2CO3, KOH, and bis(2-chloroethyl)amine hydrochloride in hot DMF. The initial product, N,N-bis[2-(2-nitrophenoxy)ethyl]formamide has been reduced to provide N,N-bis[2-(2-aminophenoxy)ethyl]formamide which after an MnII-templated cyclocondensation reaction with 2,6-diformylpyridine followed by reductive demetallation with NaBH4 gives an N,N′-diformylated 36-membered N8O4 oxaazamacrocycle.

Synthesis and thermal polymerization of aromatic 2-oxazolines containing carboxylic groups

2-(4-Carboxyphenyl)-1,3-oxazoline (2 a), 2-(3-carboxyphenyl)-1,3-oxazoline (2 b), and 2-(6-carboxynaphthyl-2-yl)-1,3-oxazoline (2 c) were synthesized by reaction of monomethyl ester chlorides of aromatic dicarboxylic acids with 2-chloroethylamine hydrochloride in the presence of triethylamine followed by cyclization with methanolic KOH. Thermal polymerization in bulk within a few minutes at 200–220°C resulted in new linear poly(ester amide)s 3 a–3 c without significant side reactions. The polymerization occurred in the melt phase (2 b) or in the solid state (2 a, 2 c) and the resulting polymers are amorphous (3 b) or semi-crystalline (3 a, 3 c). The polyaddition reactions were investigated by means of differential scanning calorimetry (DSC) and 1H NMR spectroscopy.

Synthesis of some nitrogen mustards

Nitrogen mustards with pyrimidine moiety have been synthesized by condensation of benzaldehyde mustard 7 with 4-hydroxy-2, 6-dimethyl pyrimidine, 4-chloro-2, 6-dimethyl pyrimidine. Also, N, N-bis(2-chloroethyl)amine hydrochloride, ethanolamine and diethanolamine have been condensed with 4-chloro-2, 6-dimethyl-pyrimidine respectively.

Aziridine and hydroxy- and chloroethylamine derivatives of colchicine and their biological activity

With the aim of enhancing the cytostatic properties of the initial alkaloid, new aziridine and bis(chloroethyl)amine derivatives of colchicine have been synthesized by the direct interaction of colchicine with chloroethylamine hydrochloride and also via the mono- and diethanolamine derivatives. The structures of the compounds obtained have been studied by spectral methods. An increased radiomodifying and antitumoral activity and a decreased toxicity of the substances synthesized as compared with the initial colchicine has been shown. Results obtained in the National Cancer Institute of the USA from the study of the cytostatic activity of the bis(chloroethyl)amino derivative of 60 tumor lines are presented.

SYNTHESIS OF CHIRAL BIS-(2-CHLOROETHYL) AMINO-SUBSTITUTED 1,3,2[sgrave]3γ3 (or [sgrave]4γ5)BENZODIAZAPHOSPHORINONES; RESOLUTION, OXIDATION REACTIONS AND X-RAY STRUCTURE DETERMINATIONS OF INDIVIDUAL ENANTIOMERS

The chiral N-methyl'-(1-phenylethyl)-substituted anthranilamides R-(+)-3 (R C -enantiomer) and S-(-)-3 (S C +nantiomer) were formed by reaction of N-methylisatoic anhydride, 1, with R-(+)-and S-(-)-1-phenylethylamine, R-(+)-2 and S-(-)-2. Reaction of R-(+)-3 and S-(-)-3 with phosphorus trichloride led to mixtures of diastereomers of 5.6-benzo-2-chloro-l-methyl-3-(1-phenylethyl)-1, 3, 2[sgrave]3γ3-diazaphosphorin-4-ones, (R C , S P )-4/(R C , R P )-4 and (S C , R P )-4/(S C , S P )-4. Attempted separation of the diastereomers of 4 by several methods failed. Reaction of the mixtures of (R C , S P )-4/(R C , R P )-4 and (R C , S P )-4/(S C , S P ),-4 with bis-(2-chloroethyl)amine hydrochloride in the presence of uiethylamine again led to mixtures of diastereomers of 5.6-benzo-2-[bis-(2-chloroethyl)amino]-1-methyl-3-(l-phenylethyl)-l, 3, 2[sgrave]3γ3-diazaphosphorin-4-one, (R C , S P )-5/(R C , R P )-5 and (S C , R P )-5/ (S C , S P )-5. By recrystallization it was possible to isolate the pure diastereomers (R C , S P )-5 and (S C , R P )-5. Oxidation reactions on (R C , S P )-5 and (S C , R P )-5 by the hydrogen peroxide-urea 1:1-adduct ((NH2)2C(:O).H2O2) or elemental sulfur led to the formation of the corresponding 2-oxo- and 2-thio-substituted 5, 6-benzo-1, 3, 2[sgrave]4γ5-diazaphosphorin-4-ones, (R C , R P )-6, (S C , S Pp )-6, (R C , R P )-7 and (S C , S P )-7 as pure diastereomers in each case. All compounds were characterized unambiguously by n.m.r.-spectroscopy, mass spectrometry and elemental analysis. Optical rotations were determined for most of the reaction products described. For compounds (R C , S P )-S, (R C , R P )-6, (S C , S P )-6 and (R C , R P )-7, X-ray crystal structure analyses were conducted. In all cases the absolute configuration at phosphorus was determined. The enantiomers of 6 crystallize in different space groups because only the (R C , R P ) form contains solvent of crystallization.

Rapid and efficient synthesis of 1-arylpiperazines under microwave irradiation

1-Arylpiperazines, finding wide applicability in pharmaceuticals were synthesized easily under microwave irradiation from bis(2-chloroethyl)amine hydrochloride and substituted anilines without any solvent. The reaction time was just 1–3 mins. 1-Arylpiperazines were synthesized in 53 to 73% yields. Potent serotonin ligands like Trifluoromethylphenylpiperazine (TFMPP) and 3-Chlorophenylpiperazine (mCPP) were also prepared in just 1 min. and 2 mins. respectively.

N-PHOSPHORYLATED NITROGEN MUSTARDS; PREPARATION OF 2-CHLOROETHYL- AND BIS(2-CHLOROETHYL)-AMIDES WITH THE BENZODIAZAPHOSPHORINONE RING SYSTEM

The reaction of isatoic acid anhydride 1 with NaH/BrCH2CH2Cl furnished the N-(2-chloroethyl) substituted derivative 2, which was allowed to react with methylamine to form N-(2-chloroethyl)-N′ methylanthranilamide 3, Treatment of 3 with PCI3 furnished the 1,3,2-diazaphosphorin-4-one 4, which reacted with bis(2-chloroethyl) amine hydrochloride to form the P-bis(2-chloroethyl) amino derivative 5 by substitution at phosphorus. Oxidation of 5 with the hydrogen peroxide/urea 1:l adduct led to the phosphoryl species 6, Theσ4P-derivative 7 was formed by hydrolysis of 4 with small amounts of water. Treatment of the P-chloro derivative 8 with (CH3)3SiOCH3 furnished the methoxy-substituted compound 9, which formed the phosphoryl derivative 10 upon reaction with SO2Cl2. The previously known bis(2-chloroethyl)amino-substituted 1,3,2-benzodiazaphosphorin-4-on-2-oxide 11 was synthesized by reaction of 10 with bis(2-chloroethyl) amine hydrochloride/triethylamine. The P-2-chloroethylamino-substituted derivative 12 was obtained by treatment of 8 with 2-chloroethylarnine hydrochloride/triethylamine. The structures of 3, 4 and 5 were confirmed by single crystal X-ray structure determination. In 3 the molecules are linked into chains by hydrogen bonds of the form N-H···O=C between amide groups. The heterocycles of 4 and 5 display half-boat conformation with the P atom out of plane.

PREPARATION OF N-PHOSPHORYLATED NITROGEN MUSTARDS WITH THE BENZODIAZA- AND OXAZAPHOSPHORINONE RING SYSTEMS;HYDROLYSIS OF 2-CHLORO BENZODIAZAPHOSPHORINONES

Abstract The reaction of N-p-ethoxyphenylanthranilic acid 1 with phosphorus trichloride furnished the 2-chloro-1,3,2-benzoxazaphosphorin-6-one 2, which was allowed to react with bis-(2-chloroethyl)amine hydrochloride to form 3 by substitution at phosphorus. Treatment of 3 and the previously known N-p-fluorobenzyl-, N-p-chlorobenzyl- and N-o-chlorobenzyl-substiuted 1,3,2-benzodiazaphosphorin-4-ones 4–6 with the hydrogen peroxide/urea 1:1 adduct led to the phosphoryl species 7–10. The phosphoryl derivatives 14–16 were obtained by hydrolysis of the previously known λ3P-chloro derivatives 11–13 with small amounts of water. For the N-p-fluorobenzyl substituted compound 14 a single crystal X-ray structure determination showed a weak intermolecular P—H … O contact.