Detail of "2914-69-4"

Reference

Quantitative Determination of Conformer Populations: Assessment of Specific Rotation, Vibrational Absorption, and Vibrational Circular Dichroism in Substituted Butynes

Quantitative Determination of Conformer Populations: Assessment of Specific Rotation, Vibrational Absorption, and Vibrational Circular Dichroism in Substituted Butynes. 2914-69-4 is also in the experiment. He, Jiangtao; Petrovich, Ana; Polavarapu, Prasad L. (Department of Chemistry, Vanderbilt University, Nashville, TN 37235, USA). Journal of Physical Chemistry A, 108(10), 1671-1680 (English) 2004 American Chemical Society. CODEN: JPCAFH. ISSN: 1089-5639. DOCUMENT TYPE: Journal CA Section: 22 (Physical Organic Chemistry) Section cross-reference(s): 73 To evaluate the quant. agreement between the obsd. and predicted properties of sp. rotation, vibrational absorption, and vibrational CD (VCD), (+)-3-chloro-1-butyne, which is one of the smallest single conformer chiral mols., has been synthesized for the first time and its intrinsic rotation (sp. rotation at infinite diln.), vibrational absorption, and VCD have been measured. These properties have also been predicted using d. functional theory (DFT) and large basis sets, namely aug-cc-pVDZ, 6-311++G(2d,2p), and aug-cc-pVTZ. Using these exptl. and predicted properties, the abs. configuration of (+)-3-chloro-1-butyne is established as (R). The obsd. intrinsic rotation and predicted sp. rotation are obsd. to be in excellent quant. agreement. The predicted vibrational absorption and VCD spectra are in good qual. agreement with the corresponding obsd. spectra; however, the root-mean-square percent differences in integrated intensities are ~20%-30%. The conformer populations of (-)-3-butyn-2-ol in CCl4 have then been analyzed using exptl. intrinsic rotation, vibrational absorption, and VCD; the corresponding predicted properties were also obtained, using DFT and large basis sets, as for 3-chloro-1-butyne. All three properties indicate that (-)-3-butyn-2-ol exists predominantly in two different conformations in dil. CCl4 solns. Populations of these conformers detd. from the three methods are in reasonable agreement. However, the errors in populations detd. from vibrational absorption and VCD are fairly large, which indicates the need for better quant. accuracy in the predicted vibrational absorption and VCD intensities. .

Allenes and acetylenes

Allenes and acetylenes. XVI. Chiral allenic alcohols from addition-elimination reactions of acetylenes with lithium aluminum hydride. Olsson, Lars Inge; Claesson, Alf (Biomed. Cent., Univ. Uppsala, Uppsala, Swed.). Acta Chem. Scand.Chemical with cas number 2914-69-4 also plays role. There are some commonly used reagents like 2914-69-4 in this article., Ser. B, B31(7), 614-18 (English) 1977. CODEN: ACBOCV. DOCUMENT TYPE: Journal CA Section: 22 (Physical Organic Chemistry) (R)-(-)-3,4-hexadien-1-ol, (-)-2,3-pentadien-1-ol and (-)-2-methyl-3,4-hexadien-2-ol with the max. enantiomeric purities of 75, 90-95 and 90%, resp., were formed in LiAlH4 reactions of monotetrahydropyranyl derivs. of the appropriate chiral acetylenic diols. (S)-(-)-4-methoxy-2-pentyn-1-ol was also used in the same reaction. Resolved (S)-(-)-3-butyn-2-ol was used as the starting material. The allene-forming reactions proceed via a trans-addn. of LiAlH4 across the triple bond followed by a highly anti-selective 1,2-elimination of metal alkoxide. The overall stereoselectivity increases with the donor properties of the solvent, from (Me2CH)2O through Et2O to THF. ..