441. Compounds containing the 3-chloroallyl group

Childs, A. F.; Plant, S. G. P.; Tompsett, A. L. L.; Weeks, George.

doi:10.1039/jr9480002180

Cited by 4 publications

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“…23,28 However, to our knowledge, the reaction of an allylic stannane with arsenic halide has never been described and only few allylic chloroarsines have been reported. 22,29 We observed that the reaction of allylic stannanes with arsenic chloride and without solvent was very fast at room temperature; 2-propenyl-(3a) and methallyldichloroarsine (3b) were prepared in good yields (≈75%) (Scheme 2). In the presence of AsCl 3 , the (Z)-and (E)crotyl-(1c,c′) and prenylstannane (1d) led without isomerization to, respectively, 1-methyl-2-propenyl-(3c) and 1,1-dimethyl-2-propenyldichloroarsine (3d) when the reaction was performed at -20 °C.…”

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confidence: 99%

Allylation of Phosphorus, Arsenic, and Antimony Trihalides by Allylic Stannanes. Synthesis, Spectroscopic Characterization, and Quantum Chemical Investigations of Allylic Phosphines, Arsines, and Stibines

Serre¹,

Guillemin²,

Kárpáti³

et al. 1998

J. Org. Chem.

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The reaction between an allylic tributylstannane and a phosphorus, arsenic, or antimony trihalide led to the corresponding allylic phosphine, arsine, or stibine dihalides. With phosphorus derivatives, only the gamma-regioselection was observed, as shown by the formation of (1-methyl-2-propenyl)- (2e,f)or (1,1-dimethyl-2-propenyl)dihalophosphines (2g,h) starting from crotylstannanes 1c,c' or prenylstannane 1d, respectively, and PCl(3) or PBr(3). On heating at 80 degrees C, some of these phosphines led to the corresponding thermodynamic products. Allylic dichloroarsines 3a-d were also prepared and kinetic compounds 3c,d completely rearranged at room temperature into the corresponding crotyl- (3e,e') and prenyldichloroarsines (3f). For antimony derivatives, even at low temperature (-90 degrees C), crude mixtures containing only the thermodynamic products were observed. While allylic dihalophosphines and -arsines are not efficient allylation reagents of electrophiles, allylic dichlorostibines 4a,c reacted with benzaldehyde to lead to the corresponding homoallyl alcohols. Syn and anti products were mainly produced starting from crotyldichlorostibines (4e,e'). The primary allylic phosphines 7a-f, arsines 8a-f, and stibines 9a,bhave been prepared by the chemoselective reduction of the corresponding allylic dihalophosphines, -arsines, or -stibines with LAH in tetraglyme or with Bu(3)SnH as reducing agent and characterized by (1)H and (13)C NMR spectroscopy and mass spectrometry. The primary allylic arsines and stibines are the first elements of new classes of compounds. Several allylic phosphines and arsines were investigated by ab initio quantum chemical methods and photoelectron spectroscopy. The most stable structure of these compounds is when the C-E (E = P, As) bond is out of the plane of the allyl system. This conformation is stabilized by the hyperconjugation between the pi-orbital and the C-E sigma-bond. Due to this geometrical arrangement, the phosphorus (arsenic) lone pair interacts strongly and unprecedently with the pi-system. The strength of this interaction is due to the close proximity of the pi and the n(P) (n(As)) levels.

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Section: Resultsmentioning

confidence: 99%

Allylation of Phosphorus, Arsenic, and Antimony Trihalides by Allylic Stannanes. Synthesis, Spectroscopic Characterization, and Quantum Chemical Investigations of Allylic Phosphines, Arsines, and Stibines

Serre¹,

Guillemin²,

Kárpáti³

et al. 1998

J. Org. Chem.

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Isothiocyanate derivatives of soybean oil triglycerides: Synthesis, characterization, and polymerization with polyols and polyamines

Çaylı¹,

Küsefoǧlu

2009

J of Applied Polymer Sci

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In this article, a novel two step synthesis of soy oil based isothiocyanate is described. Allylicaly brominated soybean oil (ABSO) was reacted first with ammonium thiocyanate in tetrahydro furan to form allylic thiocyanates. These compounds were then converted to isothiocyanated soybean oil (ITSO) by a thermal rearrangement. Conversion was found to be 70%. The structure of the ITSO was characterized by IR and 1 H-NMR techniques. Then ITSO was reacted with ethylene glycol, glycerol, and castor oil to produce polythiourethanes and ethylene diamine and triethylene tetra amine to produce polythioureas. Thermal properties of the products were determined by DSC and TGA techniques. DSC traces showed T g 's for ethylene glycol polythiourethane at À39 and 58 C, for glycerol polythiourethane at À39 and 126 C, for castor oil polythiourethane at À38 C and À17 C, for ethylene diamine polythiourea at À45 C, and for triethy-lene tetra amine poly thiourea at À39 C. Additionally, DSC analysis of polythioureas showed an endotherm at around 100 C. All of the polymers started to decompose around 200 C. Tensile properties of the polymers were determined. Polythiourethanes showed higher tensile strength and lower elongation when compared with their urea analogs. Stress at break values of the polymers were 1.2 MPa for glycerol polythiourethane, 0.6 MPa for ethylene glycol polythiourethane, 0.5 MPa for ethylene diamine polythiourea, and 0.9 MPa for triethylene tetra amine polythiourea polymers. Unfortunately, polymers synthesized showed poor solvent resistance. All polymers swelled and disintegrated in CH 2

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Synthese 2‐substituierter 3‐Methylen‐eycloalkene

Schulze

Richter

1983

Zeitschrift fuer Chemie

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441. Compounds containing the 3-chloroallyl group

Cited by 4 publications

References 0 publications

Allylation of Phosphorus, Arsenic, and Antimony Trihalides by Allylic Stannanes. Synthesis, Spectroscopic Characterization, and Quantum Chemical Investigations of Allylic Phosphines, Arsines, and Stibines

Allylation of Phosphorus, Arsenic, and Antimony Trihalides by Allylic Stannanes. Synthesis, Spectroscopic Characterization, and Quantum Chemical Investigations of Allylic Phosphines, Arsines, and Stibines

Isothiocyanate derivatives of soybean oil triglycerides: Synthesis, characterization, and polymerization with polyols and polyamines

Synthese 2‐substituierter 3‐Methylen‐eycloalkene

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