Cyclopropyl Chloride Research Articles

Cobalt-Catalyzed Enantioselective Reductive Addition of Ketimine with Cyclopropyl Chloride to Construct the Chiral Amino Esters Bearing Cyclopropyl Fragments

Chiral amino acid derivatives containing cyclopropyl fragments are a high-value drug candidate, but their synthesis is still challenging. We herein report an efficient construction of chiral α-tertiary amino acid deriatives...

ChemInform Abstract: Synthesis of Vinylcyclopropanes via Palladium‐Catalyzed Coupling of Cyclopropylzinc Halides with Vinyl Iodides. Total Syntheses of (.+‐.)‐Prezizanol and (.+‐.)‐Prezizaene.

AbstractThe key step in the synthesis of the sesquiterpenes (V) is the coupling of the fused cyclopropyl chloride (II) with the vinylic iodide (III) in the presence of a Pd catalyst via lithiation of (II) and formation of the corresponding organozinc chloride.

Reactions of cyclopropyl chlorides with metals and lithium naphthalene radical anion and dianion

Reactions of cyclopropyl chlorides with metals and lithium naphthalene radical anion and dianion

ChemInform Abstract: ON THE ELECTRONIC AND MOLECULAR STRUCTURES OF METHYL CHLORIDE, CYCLOPROPYL CHLORIDE AND 1,1‐DICHLOROCYCLOPROPANE

Abstract Ab initio SCF—MO calculations have been carried out on cyclopropyl chloride and 1,1-dichlorocyclopropane, to illuminate the effect of the substituent upon the cyclopropane ring. For cyclopropyl chloride, reasonable agreement is found with experimental findings. For 1,1-dichlorocyclopropane, excellent agreement is found with the results from a recent NMR study. As a means of studying the effect of a change in basis set, calculations are also carried out on methyl chloride.

ChemInform Abstract: THE CHEMISTRY OF SMALL‐RING COMPOUNDS. PART 39. DISPLACEMENTS IN CYCLOPROPYL CHLORIDES ACTIVATED BY ELECTRON‐DONATING SUBSTITUENTS

AbstractDas Chlorid (Ia) geht bei ‐30 °Cmit Methanol über das Ion (IIa) in den Diether (IIIa) über.

On the electronic and molecular structures of methyl chloride, cyclopropyl chloride and 1,1-dichlorocyclopropane

Ab initio SCF—MO calculations have been carried out on cyclopropyl chloride and 1,1-dichlorocyclopropane, to illuminate the effect of the substituent upon the cyclopropane ring. For cyclopropyl chloride, reasonable agreement is found with experimental findings. For 1,1-dichlorocyclopropane, excellent agreement is found with the results from a recent NMR study. As a means of studying the effect of a change in basis set, calculations are also carried out on methyl chloride.

Photochemical transformations. XVIII. Stereochemistry of the photosensitized rearrangements of some cyclic allylic chlorides to bicyclic (cyclopropyl) chlorides

Photochemical transformations. XVIII. Stereochemistry of the photosensitized rearrangements of some cyclic allylic chlorides to bicyclic (cyclopropyl) chlorides

The chemistry of small‐ring compounds. Part 39. Displacements in cyclopropyl chlorides activated by electron‐donating substituents

AbstractCyclopropyl chlorides with a methoxy‐ or a p‐tolyl group linked to the same carbon atom as halogen undergo substitutions in polar solvents with relatively little ring rupture, when the nucleophile is sufficiently reactive (e.g. methanol, N−3, Br−) to trap the intermediate α‐substituted cyclopropyl cations.Such substitution reactions are of the SN1 type and do not proceed via cyclopropene intermediates. With poor nucleophiles such as NO−3 in aqueous acetone, only polymeric ring‐opened products are formed.

ChemInform Abstract: THE CHEMISTRY OF SMALL RING COMPOUNDS. PART 32. SYNTHESIS OF SOME 1‐ARYLCYCLOPROPANOLS AND 1‐ARYLCYCLOPROPYL CHLORIDES

AbstractAus den Ketonen (Ia) werden über die Stufen (IIa) und (IIIa) die Cyclopropanole (IVa) bzw. Cyclopropylchloride (Va) erhalten.

Nematic phase nuclear magnetic resonance spectra and vibrationally averaged structures of cyclopropyl chloride, bromide, and cyanide

The nmr spectra of partially oriented cyclopropyl chloride, bromide, and cyanide have been analysed and the relative proton structure corrected for vibrational effects. The proton structures provide indirect evidence in support of Hoffmann's theory of substituent effects in cyclopropane rings. The distance between protons on the same side of the ring as the substituent is less than the corresponding distance on the other side. The direction of the principal orientation axis in two nematic solvents EBBA and MBBA is the same but the anisotropy of alignment is less in MBBA.

The chemistry of small ring compounds. Part 32: Synthesis of some 1‐arylcyclopropanols and 1‐arylcyclopropyl chlorides

AbstractThe synthesis of some cyclopropanes with a trimethylsilyloxy group and an aryl group carrying electron‐donating substituents at the same ring carbon atom is described. These compounds can be used as precursors for 1‐aryl‐cyclopropanols and ‐cyclopropyl chlorides.

The rearrangement of cyclopropyl chlorides to allyl chlorides : Stereospecificity in the recapture of the chloride ion

The cyclopropyl chlorides ( 1 and 2) rearrange on heating to give stereospecifically the allyl chlorides ( 3 and 4, respectively). In the presence of nucleophiles such as methoxide ion, the corresponding allyl ethers ( 5 and 6, respectively) are formed. Analysis of the stereochemistry of these products indicates that they are formed from the corresponding allyl chlorides ( 3 and 4), which are evidently the first-formed products of the reaction even in the presence of strong nucleophiles. The reaction of the allyl chlorides ( 3 and 4) with sodium phenylthioxide in aprotic non-polar solvents goes predominantly with retention of configuration, but in methanol is normal in giving predominantly inversion of configuration.

The rearrangement of cyclopropyl chlorides to allyl chlorides: stereospecificity in the recapture of the chloride ion

Abstract The cyclopropyl chlorides (1 and 2) rearrange on heating to give stereospecifically the allyl chlorides (3 and 4, respectively). In the presence of nucleophiles such as methoxide ion, the corresponding allyl ethers (5 and 6, respectively) are formed. Analysis of the stereochemistry of these products indicates that they are formed from the corresponding allyl chlorides (3 and 4), which are evidently the first-formed products of the reaction even in the presence of strong nucleophiles. The reaction of the allyl chlorides (3 and 4) with sodium phenylthioxide in aprotic non-polar solvents goes predominantly with retention of configuration, but in methanol is normal in giving predominantly inversion of configuration.

Microwave Spectrum of Cyclopropyl Bromide

The microwave spectra of four isotopic species of cyclopropyl bromide, namely C3H579Br, C3H581Br, C3H4D79Br, and C3H4D81Br have been analyzed in the frequency region of 19 000–31 000 Mc/sec. The rotational constants obtained are as follows (given in megacycles per second): ABCC3H579Br16 504.9 ± 652579.87 ± 0.032457.68 ± 0.03C3H581Br16 239.6 ± 1602560.49 ± 0.032440.12 ± 0.03C3H4D79Br15 139.2 ± 792527.52 ± 0.042455.93 ± 0.05C3H4D81Br15 046.8 ± 1842502.84 ± 0.052430.73 ± 0.04 Two structures compatible with these data have been obtained for this molecule. Structure I was calculated by assuming for the hydrogen parameters values obtained for cyclopropyl chloride, whereas Structure II was derived with the assumption that all d C–C = 1.080 Å and the ∠H–C–H's are bisected by the ring. Structure IAssumedCalculatedd C–H(trans): 1.086 Åd C1–C2: 1.521 ± 0.004 Åd C–H(cis): 1.074 Åd C1–C3: 1.512 ± 0.007 Åd C–H(sec): 1.078 Åd C3–Br: 1.905 ± 0.007 Å∠C2–C1–H(cis): 116°50′∠H(sec)–C3–Br: 116° ± 50′∠C2–C1–H(trans): 118°56′∠C2–C3–Br: 118°54′ ± 1.0°∠C3–C1–H(cis): 115°20′∠H(cis)–C1–H(trans): 115°59′ Structure IIAssumedCalculatedd C–H: 1.080 Åd C1–C2: 1.518 ± 0.004 Å∠C2–C1–H(cis): 117°37′d C1–C3: 1.507 ± 0.010 Å∠C2–C1–H(trans): 117°37′d C3–Br: 1.899 ± 0.005 Å∠C3–C1–H(cis): 117°6′∠H(sec)–C3–Br: 115°15′ ± 50′∠H(cis)–C1H(trans): 116°∠C2–C3–Br: 119°30′ ± 1.0° The analysis of the hyperfine structures of the spectra gives the following quadrupole coupling constants. For C3H579Br eQqm = 462.3 ± 3.5 Mc/sec, η = −0.23 ± 0.04; C3H581Br eQqm = 391.2 ± 1.0 Mc/sec, η = −0.20 ± 0.02; C3H4D79Br eQqm = 451.0 ± 14 Mc/sec, η = −0.24 ± 0.12; C3H4D81Br eQqm = 404.1 ± 4 Mc/sec, η = −0.08 ± 0.10. The ionicity of the bond was estimated to approximately 22%.

Microwave Spectrum, Structure, and Quadrupole Coupling Constants of Spiropentyl Chloride

The microwave spectra of C5H735Cl and C5H737Cl have been observed and analyzed. If the spiropentane ring is assumed to be in the D2d configuration, with methylene-group parameters similar to cyclopropyl chloride, the following parameters are calculated from the observed moments of inertia: r(CCl)=1.74 Å, r(CC)=1.51 Å, and ∠RCCl=118°. The quadrupole coupling constants in the inertial axis system have been obtained for both isotopic species. For the 35Cl species, the values are χaa=−30.98 MHz, χbb=6.22 MHz, and χcc=24.76 MHz. Evidence is presented which indicates that the chemical bond linking the chlorine to the ring is not axially symmetric and does not lie along the C–Cl internuclear line.

Bridged Polycyclic Compounds. XXXI. Stereochemical Aspects of the Solvolysis of Cyclopropyl Chlorides1

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTBridged Polycyclic Compounds. XXXI. Stereochemical Aspects of the Solvolysis of Cyclopropyl Chlorides1Stanley J. Cristol, R. M. Sequeira, and C. H. DePuyCite this: J. Am. Chem. Soc. 1965, 87, 17, 4007–4008Publication Date (Print):September 1, 1965Publication History Published online1 May 2002Published inissue 1 September 1965https://doi.org/10.1021/ja01095a057RIGHTS & PERMISSIONSArticle Views229Altmetric-Citations55LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (278 KB) Get e-Alerts Get e-Alerts

Molecular Structure of Cyclopropyl Chloride

The pure rotational microwave spectra of seven isotopic species of cyclopropyl chloride have been examined and rotational constants assigned. The data are sufficient for a complete structure determination by the substitution method. The bond distances and bond angles obtained are r(C1C2)=1.513 Å, r(C2C3)=1.515 Å, r(CCl)=1.740 Å, average r(CH)=1.08 Å, ∠CCCl=118.7°, ∠ClCH=115.8°, and ∠HCH=116.2°. The quadrupole coupling constants of C3H5Cl35 in the principal inertial axis system are χaa=—56.64 Mc/sec, χbb=36.72 Mc/sec, and χcc=19.92 Mc/sec. These values are consistent with χzz=—71.4 Mc/sec, and ηbond=0.029 if the z axis and the CCl internuclear line are assumed to coincide, and with χzz=—73.5 Mc/sec if the charge distribution near the chlorine nucleus is assumed to be cylindrically symmetric.

Microwave Studies of the Structure of Cyclopropyl Derivatives

The microwave spectra of cyclopropyl chloride and cyclopropyl cyanide have been studied and rotational constants for the Cl35 and Cl37 molecules of the chloride and for the normal molecule and two deuterated species of the cyanide have been determined. The two deuterated species are the cis and trans forms of C lim |H2–CHD–C lim |¯H–CN. For C3H5Cl35, A = 16 625±145 Mc, B = 3905.4±0.3 Mc, and C = 3622.5±0.3 Mc. For C3H5Cl37, A = 16085±415, B = 3810.4±0.5 Mc, and C = 3540.8±0.5 Mc. The following structure fits the rotational constants within the experimental errors: dC–C = 1.5131 A, dC–Cl = 1.7780 A, dC–H = 1.105 A, ≰HCH = 114°36′, ≰HCCl = 120°52.9′. For C3H5CN, A = 15 917 Mc, B = 3465.06 Mc, and C = 3286.22 Mc. For cis C3H4DCN, A = 14 543 Mc, B = 3419.34 Mc, and C = 3229.15 Mc. For trans C3H4DCN, A = 15 367 Mc, B = 3358.79 Mc, and C = 3161.26 Mc. The following structure fits the rotational constants B and C to an average of 1.5 Mc: dC–C(ring) = 1.5131 A, dC–C(CN) = 1.4679 A, dC–H = 1.112 A, dC≡N = 1.1574 A, ≰H–C–H = 115°35′, and ≰C(CN)−C−−H=119∘35′. Analysis of the quadrupole structure in C3H5Cl shows that eqQ along the C–Cl bond axis is —71.7 Mc for Cl35, indicating 23% ionic character. The asymmetry η = 0.156 for Cl35 indicates a double bond character of 4%.

Reaction of Cyclopropyl Chloride with Lithium. Isolation of Dicyclopropyl

Reaction of Cyclopropyl Chloride with Lithium. Isolation of Dicyclopropyl

Cyclopropane Derivatives. II. The Electric Moments of Some Alicyclic Compounds

There is considerable evidence that compounds in which a cyclopropane ring is located adjacent to an unsaturated linkage, such as a carbonyl group or double bond, exhibit many of the physical and chemical properties characteristic of substances containing conjugated double bonds. For example, the absorption spectrum of a double bond conjugated with a cyclopropane ring is shifted toward longer wave lengths, the shift being somewhat less than that observed for conjugated double bonds and a detailed investigation of three type reactions showed that a cyclopropane ring conjugated with a carbonyl group behaved in a manner not fundamentally different from the corresponding α,β-unsaturated carbonyl compounds. Since conjugation usually has a considerable effect on electric dipole moment, we have determined the electric moments of cyclopropyl chloride, cyclopropylidene chloride and cyclopropyl cyanide for comparison with those of the corresponding cyclopentyl compounds in which conjugation was expected to be unimportant. The moments of some other cyclopentyl derivatives which have not been reported previously were also determined.