Hydrogenolysis of Alkyl Halides by Lithium Aluminum Hydride<sup>1</sup>

Johnson, James E.; Blizzard, Ronald H.; Carhart, Homer W.

doi:10.1021/ja01191a035

Cited by 71 publications

(19 citation statements)

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“…Alkyl halides can be reduced by LiAlH 4 in ethereal solvents; however, the rates of reduction markedly decrease from iodide to bromide to chloride (I > Br > CI) and from primary > secondary > tertiary halides, thus defluorination was not expected to be significant (Johnson et al, 1948). In fact, a kinetic study of LiAlH 4 reductions at room temperature in THF with various alky halides illustrated that cyclopentyl bromide, which is a more reactive model for the cyclopentyl fluoride 2 , underwent only 11% reduction after 30 min at room temperature and required 24 h to fully reduce (Krishnamurthy and Brown, 1982).…”

Section: Discussionmentioning

confidence: 99%

Fully-automated synthesis of 16β- 18 F-fluoro-5α-dihydrotestosterone (FDHT) on the ELIXYS radiosynthesizer

Lazari

Lyashchenko

Burnazi

et al. 2015

Applied Radiation and Isotopes

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Noninvasive in vivo imaging of androgen receptor (AR) levels with positron emission tomography (PET) is becoming the primary tool in prostate cancer detection and staging. Of the potential 18F-labeled PET tracers, 18F-FDHT has clinically shown to be of highest diagnostic value. We demonstrate the first automated synthesis of 18F-FDHT by adapting the conventional manual synthesis onto the fully-automated ELIXYS radiosynthesizer. Clinically-relevant amounts of 18F-FDHT were synthesized on ELIXYS in 90 min with decay-corrected radiochemical yield of 29 ± 5% (n = 7). The specific activity was 4.6 Ci/µmol (170 GBq/µmol) at end of formulation with a starting activity of 1.0 Ci (37 GBq). The formulated 18F-FDHT yielded sufficient activity for multiple patient doses and passed all quality control tests required for routine clinical use.

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Section: Discussionmentioning

confidence: 99%

Fully-automated synthesis of 16β- 18 F-fluoro-5α-dihydrotestosterone (FDHT) on the ELIXYS radiosynthesizer

Lazari

Lyashchenko

Burnazi

et al. 2015

Applied Radiation and Isotopes

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“…at room temperature. These mild conditions were used to minimize substitution of the chlorine with hydrogen (Johnson, Blizzard & Carhart, 1948). After decomposing the excess of reagent with water, the products were extracted with ether.…”

Section: Haloesters Produced By M Cerijicans =47mentioning

confidence: 99%

Production of -Haloesters from Alkyl Halides by Micrococcus cerificans

Kolattukudy¹,

Hankin

1968

Journal of General Microbiology

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S U M M A R YMicrococcus cerzjicans grows with n-alkyl chlorides and bromides containing 16 to 20 carbon atoms as the sole source of carbon and forms waxy esters. The esters produced from n-Hexadecyl chloride were identified to be I 6-chlorohexadecyl-I 6-chlorohexadecanoate (74 %) and I 6-chlorohexadecylhexadecanoate (23 %). More than 80 % of the fatty acids of the more polar cellular lipids also contained chlorine at the w-carbon. These results show that the mechanism of utilization of alkyl halides by this organism is similar to that of alkanes and the initial attack is specifically at the non-halogenated methyl carbon.

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“…Lithium aluminum hydride, like Grignard reagents, also reacts with compounds other than those containing active hydrogen, It will reduce aldehydes, ketones, carboxylic acids, esters, acid chlorides and acid anhydrides (115,116), alkyl halides (69,117), quinones, nitriles, nitro compounds, azoxy compounds, aldinlines, epoxides, and amides (117'), amino acid esters (71), chlorosubstituted acids and acid derivatives (155), cyclic quaternary ammonium salts (144), and sulfones (11). The stoichiometry of these reductions requires 0.25 mole of lithium aluminurn hydride per mole of aldehyde or ketone, 0.50 for esters and acid chlorides, 1.00 for acid anhydrides, 0.50 (in addition to 0.25 rnole for active hydrogen) for carboxyl groups (11.5, 116), 0.50 for nitriles (1831, and 0.25 for alkyl halides (69).…”

Section: Llthium Aluminum Hydridementioning

confidence: 99%

“…The stoichiometry of these reductions requires 0.25 mole of lithium aluminurn hydride per mole of aldehyde or ketone, 0.50 for esters and acid chlorides, 1.00 for acid anhydrides, 0.50 (in addition to 0.25 rnole for active hydrogen) for carboxyl groups (11.5, 116), 0.50 for nitriles (1831, and 0.25 for alkyl halides (69). The literature indicates varying degrees of completeness for these reactions by refluxing in various ethers.…”

Section: Llthium Aluminum Hydridementioning

confidence: 99%

“…perature, tetrahydrofuran (boiling point 65 -66" C.) and di-n-butyl ether (boiling point 140.9' C.) ale suitable, although external temperature control is necessary with the latter solvent to prevent decomposition of the reagent above 100" C. (69). Hochstein (58) found N-ethylmorpholine more satisfactory than dibutyl ether; dioxane, anethole, and K-methylmorpholine were less satisfactory.…”

Section: Llthium Aluminum Hydridementioning

confidence: 99%

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Determination of Reactive Hydrogen in Organic Compounds

Olleman¹

1952

Anal. Chem.

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Methods for quantitatively determining reactive hydrogen in organic compounds have been reviewed to find the most suitable procedures for estimating the reactive structural units in coal degradation products. In the past, reaction with methylmagnesium iodide or lithium aluminum hydride has been used to determine total reactive hydrogen in organic compounds with an accuracy o f 1 3 to 5%. The types of compounds which have been determined are: alcohols, phenols, enols, mercaptans, acids. amines, amides, and water. Acylation methods. including acetylation, phthaloylation, benzoylation, ETHODS for quantitatively determiningreactive hydrogen in organic compounds-Le., hydrogen attached tonitrogen. oxygen, or sulfur and exceptionally reactive carbon-hydrogen structures-have been reviewed to find the most suitable procedures for estimating the reactive oxygen-and nitrogen-containing structures in coal degradation products. The chemical literature from 1927 to 1949, inclusive, has been thoroughly searched, and some earlier and more recent references have been consulted The literature previous to 1931 was reviewed by Meyer (93).Methyl Grignard reagents and lithium aluminum hydride will react quantitatively R ith reactive hydrogen atoms in organic compounds t o form methane and hydrogen, respectively. The gaa formed in each case is a memure of the "artive hydrogen." Other reagents have been reported for the determination of active hydrogen but are generally less satisfactory.Some of the active hydrogen atoms can also be replaced b i a(-yl groups, and compounds containing such hydrogen atoms are said to contain "acylatable hydrogen" or usually "acetylatable hydrogrn." ""wylatable hydrogen" and ' acetylatable hydrogen"are not strictly correct t e i m~, inaqmuch as the hydrogen is not acylated but rather replaced by an acyl group. However, these are convenient ternis which distinctly differentiate methods which involve acylation of reactive groups from the methods I T hich determine total "active hydrogen." Different reagents and conditions cause quantitative acylation of different functional groups, and consequently the terms "acylatable hydrogen" and "acetylatahle hydrogen" have little meaning unless the reagent and conditions are specified. Pa 1 Present addreas, Verona Research Center Koppers Co , Inc , Verona,formylation, and stearylation, vary greatly among themselves and give results depending on reagents and conditions. Variations of the most common method-i.e., acetylation using acetic anhydride and pyridine at approximately 100' C.-have been used to determine primary and secondary alcohols, "unhindered" phenols, and primary and secondary amines. Other acylation reagents may be advantageous if tertiary alcohols or pyrroles must be determined or selectivity of reaction is desired. Applicability of different acylation methods for determining functional groups has been tabulated.The methods of deterniining reactive hydrogen have thus been divided into two major groups-determinations of active hydrogrn and determinations o...

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Hydrogenolysis of Alkyl Halides by Lithium Aluminum Hydride¹

Cited by 71 publications

References 0 publications

Fully-automated synthesis of 16β- 18 F-fluoro-5α-dihydrotestosterone (FDHT) on the ELIXYS radiosynthesizer

Fully-automated synthesis of 16β- 18 F-fluoro-5α-dihydrotestosterone (FDHT) on the ELIXYS radiosynthesizer

Production of -Haloesters from Alkyl Halides by Micrococcus cerificans

Determination of Reactive Hydrogen in Organic Compounds

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Hydrogenolysis of Alkyl Halides by Lithium Aluminum Hydride1

Cited by 71 publications

References 0 publications

Fully-automated synthesis of 16β- 18 F-fluoro-5α-dihydrotestosterone (FDHT) on the ELIXYS radiosynthesizer

Fully-automated synthesis of 16β- 18 F-fluoro-5α-dihydrotestosterone (FDHT) on the ELIXYS radiosynthesizer

Production of -Haloesters from Alkyl Halides by Micrococcus cerificans

Determination of Reactive Hydrogen in Organic Compounds

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Product

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Hydrogenolysis of Alkyl Halides by Lithium Aluminum Hydride¹