Reaction Of Propargyl Bromide Research Articles

Application of 1- and 2-propargyl-tetrazole in laser-ignitable energetic coordination compounds

1- and 2-Propargyl-tetrazole (1- and 2-PryTz) were synthesized by reaction of propargyl bromide with sodium tetrazolate and used as ligands in energetic coordination compounds (ECCs) and evaluated concerning their thermal and mechanical sensitivities. Furthermore, the two nitrogen-rich compounds 1-((1H-1,2,3-triazol-4-yl)methyl)-1H-tetrazole (TriMT, 3) and 1-((1-(2-(1H-tetrazol-1-yl)ethyl)-1H-1,2,3-triazol-4-yl)methyl)-1H-tetrazole (TriMTET, 4) were prepared. Both were characterized by IR spectroscopy, NMR measurements, and low-temperature X-Ray diffraction analysis. Due to the highly endothermic enthalpy of formation of the propargyl-tetrazole ligands, powerful, yet relatively safe to handle, laser-ignitable ECCs were obtained.

Interplay between Conformation and Crystal Packing in Aryl Propargyl Ethers: Structural and Spectroscopic Properties of 2‐(prop‐2‐yn‐1‐yloxy)acene Derivatives

AbstractThe 2‐(prop‐2‐yn‐1‐yloxy)naphthalene (compound I) and 1‐nitro‐2‐(prop‐2‐yn‐1‐yloxy)benzene (compound II) were prepared in excellent yields by the reaction of propargyl bromide with 2‐naphthol and 2‐nitrophenol, respectively. Structural and conformational properties of both compounds have been analyzed using a combined approach including single‐crystal X‐ray diffraction and quantum chemical calculations. Two forms are found to be stable and nearly isoenergetic conformers, depending on the mutual orientation of the C≡C triple bond and the O–C single bond of the prop‐2‐yn‐1‐yloxy group. The gauche conformation is the most stable form for the vacuum isolated species, with the anti conformation higher in energy by 1.00 and 1.89 kcal/mol computed at the M06‐2X/6‐311++G(d,p) level of approximation, for I and II, respectively. The gauche form is observed in the crystal of I but the nearly planar anti conformation is adopted in the crystalline phase of compound II. The occurrence of C–H⋅⋅⋅π and C–H⋅⋅⋅O intermolecular interactions involving the acidic ‐C≡C–H hydrogen donor and ‐C≡C‐ and ‐OCH2– acceptors is discussed. Furthermore, vibrational features of the prop‐2‐yn‐1‐yloxy moiety are analyzed by infrared and Raman spectroscopy. The UV‐Vis spectrum shows the presence of well‐defined absorption at ca. 280 and 320 nm assigned to the π→π* transitions in the naphtyl/benzyl and prop‐2‐yn‐1‐yloxy groups, respectively.

Synthesis of dipyrrolo-diazepine derivatives via intramolecular alkyne cyclization

A regioselective approach was developed for the synthesis of dipyrrolo-diazepine derivatives. The synthetic route to dipyrrolo-diazepines first involves the synthesis of dipyrromethanes, followed by reaction of propargyl bromide in the presence of NaH to attach one alkyne functionality to the pyrrole nitrogen atom. Intramolecular heterocyclization with NaH in DMF between the alkyne functionality and pyrrole nitrogen atom gave the desired structures in good yields.

Microwave assisted synthesis of dihydropyrrole by AgOAc catalyzed intramolecular cyclization reaction of homopropargyl amine

A series of 5-aryl dihydropyrrole was synthesized from the intramolecular cyclization reaction of homopropargyl amine in the presence of AgOAc as catalyst under microwave irradiation reaction conditions. The homopropargyl amine was prepared by the reaction of propargyl bromide with N-tosyl aldimine under a sonochemical Barbier-type reaction condition. Further aromatization reaction of 5-aryl dihydropyrrole in KOtBu/DMSO can afford 2-aryl pyrrole under microwave irradiation reaction conditions.

(4-Ferrocenylphenyl)propargyl ether derived carbohydrate triazoles: influence of a hydrophobic linker on the electrochemical and cytotoxic properties

In this article we describe a detailed study of the influence of a hydrophobic linker on the properties of a series of ferrocene–carbohydrate conjugates. The alkyne, (4-ferrocenylphenyl)propargyl ether, was prepared from the reaction of propargyl bromide and 4-ferrocenylphenol. The structure of the alkyne was determined using a single crystal X-ray diffraction study. A benzyl triazole (3a) was synthesised for comparison purposes in the electrochemical and cytotoxic study. Herein, we report the synthesis and characterization of a series of carbohydrate triazole conjugates (3b–h) by using the Huisgen 1,3-dipolar cycloaddition reaction of a series of carbohydrate azides and (4-ferrocenylphenyl)propargyl ether. UV-visible spectroscopy and electrochemical studies were performed on the alkyne and triazole compounds. The data generated from the cyclic voltammetric studies was used to calculate the diffusion coefficients (Df) of the ferrocene–carbohydrate conjugates in DMSO and DMSO–buffer solutions. Slightly higher diffusion coefficient values were obtained for the carbohydrate triazole conjugates (3b–h) in the buffer solution, perhaps due to the hydrophobic nature of the linker and the absence of a hydrogen-bonding substituent adjacent to the ferrocene core. Furthermore, the triazole conjugate (3f) derived from ribofuranose exhibited significant cytotoxicity against a hormone dependent breast cancer cell line (MCF-7) with an IC50 value lower than 10 μM.

Synthesis of some Acetylenic Morpholine Derivatives via Grignard Reactions

New derivatives for acetylenic morpholine were prepared. Acetylenic amine (Npropargyl morpholine 1) was synthesized by the reaction of propargyl bromide with morpholine in aqueous medium. This compound was used as a synthone for hydroxy acetylenic compounds. Compound (1) was converted to the Grignard reagent (2) by the reaction with methyl magnesium iodide. The reaction of the intermediate (2) with different carbonyl compounds afforded hydroxy acetylenic compound (3). Finally, prepared Npropargyl ether morpholino (4a-i) was prepared by the reaction of the hydroxy acetylenic compound with chloro acetanilide, benzyl chloride via willamson reaction. The structure of the synthesized compounds has been elucidated by the available physical and spectral methods.

ChemInform Abstract: Dipropargyl Selenide

Abstractsynthesis by reaction of propargyl bromide with in situ generated Na2Se

Double Intramolecular 1,3-Dipolar Cycloaddition of Diazo-terminal Dialkyne: Synthesis of a New Bis(1,2,3-triazolo-1,4-oxazine)

A new bis(1,2,3-triazolo-1,4-oxazine) fused heterocyclic compound was synthesized from terminal meso-1,2,3,4-diepoxybutane via azide ring opening reaction, followed by propargylation and double 1,3-dipolar intramolecular cycloaddition. No effect on the reaction outcome was observed when Cu(I) was used as catalyst. In both cases catalyzed and uncatalyzed reactions, only the exo-tetracyclic two to two fused isomer was obtained. 1,2,3-Triazoles and oxazines, are heterocycles which constitute a large number of synthetic compounds. Applications of these heterocycles in various areas have been reported. For example, they are used as an anti-HIV, anti-allergic, antibacterial, fungicides, herbicides, paints, corrosion inhibitors, pesticides and agrochemical agents. For oxazines and their derivatives, a particular interest has emerged since the discovery of Efavirenz (trifluoromethyl-1,3-oxazin-2-one) inhibitor non-nucleoside reverse transcriptase used as a selective anti-HIV drug. On the other hand, the 1,3-dipolar azide-alkyne cycloaddition is a well known reaction which has been recently applied in the Click Chemistry. A remarkable development is potentiated by the use of catalytic metals such as (Cu) and (Ru). The majority of azide/alkyne reaction studies deal with intermolecular cycloadducts. However those related to the intramolecular processes remain limited. Furthermore, previous studies have focused on the synthesis of target and specific molecules rather than on a general systematic investigation of its potential application in organic synthesis. In the present work, we describe the synthesis of one compound having four hetrerocycles, two to two fused, in three steps starting from diepoxybutane. The preparation of the meso-diazido-dialkyne ether 2 was carried out through opening of the meso-diepoxybutane rings 1 by azide ion followed by reaction of propargyl bromide (Scheme 1). The meso-diazido-dialkyne ether 3 was obtained in satisfactory yields (81%). The meso-diazido-dialkyne 3 is unstable and decomposes on contact with air. Therefore, the mixture obtained from the propargylation reaction was diluted in situ in dry toluene and used in situ without purification in the next step. The uncatalyzed dipolar [3+2] double intramolecular cycloaddition reaction of product 3 proceeds spontaneously at room temperature, producing exclusively the exo-tetraheterocyclic compound 4. To reduce the reaction time, the mixture was heated at 50 C in toluene (A Condition). In an attempt to direct the reaction towards the formation of another polyheterocyclic compound, the reaction was performed in the presence of a catalytic amount of CuCl (5%) (B Condition). Either carried out according to A (79%) or B (75%) conditions, the double intramolecular cycloaddition reaction of diazido-dialkyne ether 3 leads always to the formation of the same isomer 4 (Scheme 1). Scheme 1. Synthesis of the meso-bis(1,2,3-triazolo-1,4-oxazine) It is worth to note that several conformers are possible for compound 3, due to the free rotation around the CH-CH central bond. Because of the free rotation around the two CH-O bonds, the stable conformation can exist in three geometric forms (a), (b) and (c). From these forms, two exo-cyclic isomers may be formed 4 and 5 (Scheme 2). The (a) form has both azide and alkyne dipoles one in face to the other with a favorable orbital overlap flatness which explain the exclusive formation of the exo-tetracyclic isomer 4. For the (b) form, the  part of favorable flatness cyclizes easily (Scheme 2). So in the  side, the propargylic group must rotate around C-O to cyclize with the second azide group and would lead once again to the isomer 4. The (c) form does not afford a favorable orbital overlap which can explain the absence of the exo-cyclic isomer 5. Therefore, (c) turns into (b) and/or (a) to give also compound 4. Scheme 2. Explication of the formation of the tetracyclic isomer 4 The H and C NMR spectral data confirm the symmetrical structure proposed. In particular the H NMR spectrum shows an AB system corresponding to the allylic protons O-CH2-C=C, appearing into 5.0 ppm (JAB = 15 Hz). Moreover, the -CH2-N protons show another AB system (JAB  12 Hz) which is partially coupled with the proton of the asymmetric carbon. ANTIBACTERIAL TEST The preliminary antibacterial activity study of compound 4 was followed by the disk diffusion method against five bacteria (Gram+ and Gram-) of widely encountered references in many human diseases. The results are given in Table 1. As can be seen from Table 1, it appears that compound 4 has no activity against Escherichia coli (DH5α), Pseudomonas aeruginosa (PAO1), Salmonella typhi (ATCC 25922) and Staphylococcus aureus (ATCC 6538). However, it presents a moderate activity against Enterococcus feacium strain ATCC (19,436) for which inhibition diameter is 11 mm. This value is the average of three experimental tries (10 mm, 11 mm

A Facile Synthesis of 2‐Imino‐4‐methylene‐1,3‐dithiolanes

AbstractA one‐pot synthesis of 2‐imino‐4‐methylidene‐1,3‐dithiolanes via a three‐component reaction of propargyl bromide (=3‐bromoprop‐1‐yne), primary amines, and carbon disulfide (CS2) is described.

6-Bromo-1-(1,2-propadienyl)-3-(2-propynyl)-1H-imidazo[4,5-b]pyridin-2(3H)-one

The reaction of propargyl bromide and 6-bromo-1,3-dihydro­imidazo[4,5-b]pyridin-2-one in refluxing dimethyl­formamide yields the title compound, C12H8BrN3O, which features nitro­gen-bound propadienyl and propynyl substituents. The imidazolopyridine fused ring is planar (r.m.s. deviation = 0.012 Å); the propadienyl chain is coplanar with the fused ring as it is conjugated with it, whereas the propynyl chain is not as the nitro­gen-bound C atom is a methyl­ene linkage. The acetyl­enic H atom is hydrogen bonded to the carbonyl O atom of an adjacent mol­ecule, forming a helical chain runnning along the b axis.

Derivatization and in situ metallation of phthalocyanines using click chemistry

Dialkyl (3,4-dicyanophenyl)propargylmalonates were prepared by the reaction of propargyl bromide and the potassium salt of dialkyl-3,4-dicyanophenylmalonates. A cyclotetramerization reaction was achieved in pentanol in the presence of DBU without protective/deprotective chemistry, affording the peripherally tetrasubstituted alkynyl phthalocyanines. Subsequently, in situ metallation and ‘clicking’ were employed for the first time as an efficient and quantitative route to tetratriazole-functionalized phthalocyanines.

Synthesis of Fréchet type dendritic benzyl propargyl ether and Fréchet type triazole dendrimer

Fréchet type dendritic benzyl propargyl ethers were synthesized by the reaction of propargyl bromide with the corresponding Fréchet type dendritic benzyl alcohol. A propargyl focal point functionalized dendrons were applied for the construction of symmetric and unsymmetric dendrimers containing 1,2,3-triazole rings as connectors via click chemistry with a tripodal azide core or a azide focal point functionalized Fréchet type dendrons.

Experimental and theoretical studies of the propargyl-allenylindium system.

The transient organoindium intermediates formed in the reaction of propargyl bromide with indium in aqueous media and tetrahydrofuran were investigated by NMR spectroscopy and found to be allenylindium(I) and allenylindium(III) dibromide. The influence of solvent and methyl substitution on the propargyl-allenylindium system was also studied. The experimental observations were supported by theoretical calculations using the B3LYP/6-311+G* method.

On pentaorganylstiborane: III. Regio- and diastereoselective additions of acetylenic and allenic organoantimony compounds to aldehydes

The reaction of propargyl bromide ( 4a) with tributylstibine gave allenyltributylstibonium bromide ( 5), and its corresponding pentaorganylstiborane reacted with aldehyde to give homopropargylic alcohol ( 10a) exclusively in good yield. However, the reaction of 1-bromo-2-butyne ( 4b) with tributylstibine gave acetylenic stibonium bromide ( 6b), and its corresponding stiborane reacted with aldehyde to give allenic alcohol ( 9b) as major product. The reaction of 3-bromo-1-trimethylsilyl-1-propyne ( 4d) with tributylstibine also gave acetylenic stibonium bromide ( 6d), but the major product of the reaction of its corresponding stiborane with aldehyde was acetylenic alcohol ( 10d), and the regioselectivity was very high in the presence of LiBr. Further, it was found that the allenic stibonium bromide ( 12) was obtained by the reaction of 3-bromo-1-butyne ( 11) with tributylstibine. The corresponding stiborane ( 13) reacted with aldehyde to give acetylenic alcohol ( 14) exclusively in good yield, and the diastereoselectivity was moderately in favour of the threo isomer in the presence of MgBr 2. All of the reactions had good chemoselectivity for aldehyde.

Reaction of Propargyl Bromide with Aldehydes in the Presence of Metallic Tin. Synthesis of Homopropargylalcohols and Homoallenylalcohols

Abstract In the presence of water, metallic tin and propargyl bromide reacted smoothly with aldehydes to give the corresponding homopropargyl alcohols (a) and homoallenyl alcohols (b). High Chemospecifity to bifounctional carbonyl compounds containing -OH, -X and -NO2 etc. was obtained.

ChemInform Abstract: Lead Promoted Barbier‐Type Reaction of Propargyl Bromide with Aldehydes.

AbstractReaction of propargyl bromide (II) with the aldehydes (I) yields a mixture of the unsaturated alcohols (III) and (IV), presumably via an active divalent organolead reagent.

The synthesis and some reactions of a series of “skipped” polyacetylenes containing terminal acetylene groups

The synthesis and some reactions of a series of linear 1,4-polyynes containing terminal acetylene groups (Ia–e) are described. Reaction of propargyl bromide (II) with ethynylmagnesium bromide (III) in the presence of CuCl gave 1,4-pentadiyne (Ia). Rearrangement of Ia with KOBu t led to 1,3-pentadiyne (IV), while treatment with Br 2 furnished 1,2,4,5-tetrabromo-1,4-pentadiene (V). Oxidation of Ia with O 2, CuCl and NH 4Cl yielded the linear dimer (VIa) [rearranged to 2,4,6,8-decatetrayne (VIII) with KOH] and linear trimer (VIb). Hydrogenation of the crude oxidation product gave saturated hydrocarbons derived from VIa, VIb, the linear tetramer (VIc) and the cyclic tetramer (VII), but none derived from the cyclic dimer or cyclic trimer of Ia. Similarly, oxidation of Ia with Cu(OAc) 2 in pyridine and subsequent hydrogenation led to saturated hydrocarbons derived from VIa and VIb, but none derived from the cyclic dimer or cyclic trimer. In order to prepare cyclodecane as a comparison compound, the cycloethylenedithioketal (X) derived from cyclodecanone was treated with Raney Ni in boiling EtOH, but the reaction led mainly to cis-cyclodecene. Treatment of 1,4-dibromo-2-butyne (XIII) with an excess of III in the presence of CuCl yielded 1,4,7-octatriyne (Ib), 1,4,7,10,13-tetradecapentayne (Id) and 1,4,7,10,13,16,19-eicosaheptayne (Ie). Rearrangement of Ib with alkaline Al 2O 3, or KOBu t at room temp gave 2,4,6-octatriyne (XVII), while treatment with boiling ethanolic KOH or KOBu t in hot Bu tOH led to 2-ethoxy-2-octene-4,6-diyne (XVIIIa) or 2- t-butoxy-2-octene-4,6-diyne (XVIIIc), respectively. 1,4,7,10-Undecatetrayne (Ic) was prepared from crude Ia by conversion to the bis-Grignard derivative, followed by reaction with propargyl bromide (II) in the presence of CuCl.