CHEM 184/284 (Chemical Literature) - Huber - Winter 2024: Beilstein and Gmelin in Print

Beilstein Handbook of Organic Chemistry

Organization of Beilstein

• Beilstein attempted to cover the entire organic chemical literature published within a given period:
• When dealing with such a huge volume of literature, the organization of such a work is necessarily complex.
• The Beilstein handbook is divided chronologically, then, within each period, divided by a chemical classification scheme.
• Chronological Organization
  • Hauptwerk (H) "Basic Series" Up to 1909
  • Ergangzungswerk (E)"Supplement"
    • E(I) - 1910-1919
    • E(II) - 1920-1929
    • E(III) - 1930-1949
    • E(IV)- 1950-1959
    • E(V) - 1960-1979
  • E(III) and E(IV) overlapped in production, so their heterocycle volumes were merged.
• Organization by Chemical Class
  • Beilstein records are for individual compounds. To facilitate browsing, related compounds are grouped into "volumes" (which may occupy several physical books).
  • The classification rules remain constant for all supplements, so if a compound is found in Vol. 22 in (H), it's in Vol. 22 in all the supplements as well.

Details of Chemical Class Organization

• To use Beilstein in print, it is necessary to know how compounds are placed into volumes.
• While there are indexes for the Handbook, they are divided by volume as well!
• The three largest divisions are:
  • Acyclics (e.g. methane, ethane) in Volumes 1-4
  • Isocyclics (e.g. cyclooctane, benzene) in Volumes 5-16
  • Heterocyclics (e.g. pyridine, THF) in Volumes 17-27
• Within the three broad groups, compounds are assigned to volumes based on the functional groups present, such as: -OH, -COOH, =O, -NH2
• In heterocycles, the number and type of ring heteroatoms is also relevant.
• See the table below for a complete summary.

Contents of the 27 Volumes of the Beilstein Handbook

Organization within Volumes

• Within each volume, compounds are arranged first in order of increasing unsaturation, e.g. ethane before ethene before ethyne.
• Then, by increasing molecular size, e.g. ethane before propane before butane.
• Then by:
  • increasing degree of substitution,
  • increasing "size" of substituents.

Choosing Between Possible Volumes

• If a compound might be placed in two or more possible volumes (e.g. it contains both a heterocyclic and an isocyclic component), then additional rules apply.
• Principle of Latest Entry -- If a compound might be located in two or more places, it will appear in the highest numbered volume of the possibilities.
• Parent Compounds vs. Derivatives -- Certain types of compounds are considered parent compounds; others as derivatives. A derivative is listed following the parent compound from which it is derived.
• The trick then becomes how to identify which is the "parent" for the compound in question.

Identifying Parent Compounds

• Three rules are used to identify parents vs. derivatives.
• Non-Functional Substitution
  • Certain groups are always considered derivative:
    • Halogens (F, Cl, Br, I)
    • Nitro (NO2), Nitroso (NO), Azido (N3)
  • The parent compound is determined by replacing the group with H or OH, depending on chemical common sense:
    • CH3CH2Cl --> CH3CH3 ...but...
    • CH3COCl --> CH3COOH
• "Chalcogen Substitution"
  • Sulfur, selenium and tellurium are "replaced" by oxygen to find the parent compounds, except in the oxyacid groups (e.g. -SO3H, -SO2H)
    • Me2S is considered a derivative of Me2O
    • Thiophene is considered a derivative of furan.
• Functional Substitution
  • Whenever two "pieces" of a compound are connected by a heteroatom (O, N, S, etc.), break it up by formal hydrolysis.
  • The resulting fragment with the "latest entry" becomes the parent compound of the starting compound. Example:
    • MeCOOMe --> MeCOOH + MeOH
    • Acetic acid is Vol.2; Methanol is Vol. 1
    • Therefore Methyl acetate is Vol. 2.
  • Another example: Feropolone (C24H32O6)
    
    
    • Step 1: "Hydrolyze" at the oxygen in the bridging chain.
      
    • Step 2: Check which key features each fragment has
      • Left: Isocycle with oxo, two hydroxy groups --> Volume 10
      • Right: Heterocycle with one ring O, oxo and hydroxy groups --> Volume 18
    • By Principle of Latest Entry, the fragment which appears in Volume 18 controls the entry for the compound as a whole.
    • Step 3: Go to Volume 18 and check the appropriate name or formula index.
  • For more detailed description and more examples, see How to Use Beilstein, SEL Ref Area QD251.B43 B45 1978.
• Remember to always use the easy way when you can! Many sources, including the Aldrich Catalog, CRC Handbook, HODOC, Merck Index, etc. give references to the Beilstein Handbook and their indexes are easier to use! Note that they will usually only give the reference for one of the supplement series - but once you have the basic volume, tracking the compound to its other Beilstein references is easy.

Beilstein Record Content

• A compound record in Beilstein will cover all the published data on the compound within the appropriate period.
• Therefore, the amount of information in a given compound's record is dependent on the amount of research done; old data is not repeated.
  • Example: Pyridine , in E(V) 1960-79, has a 19 page entry, plus an additional 38 pages of salts and addition compounds.
• Some physical data -- mp, bp, density, etc. -- is given directly.
• Preparations are summarized.
• References only are given for some info.
• Remember that in H-E(IV), all text is in German. Also, in those volumes, journal abbreviations are in Beilstein style, e.g. B for Chemische Berichte, Am. Soc. for JACS
• If you need help with the German terms/abbreviations, see the Beilstein dictionary at http://www-sul.stanford.edu/depts/swain/beilstein/bedict1.html.

Gmelin Handbook of Inorganic and Orgamometallic Chemistry

Organization of Gmelin

• Gmelin published print volumes entirely according to editorial choice, reflecting mainly the volume of research in a given area since the last such volume.
• Gmelin does not attempt to cover chronological periods in a block. Each volume is devoted to a particular aspect of the chemistry of a single element, with a specified closing date. Examples:
  • Magnesium has had eight volumes published -- none since 1952.
  • Iron has had over 30 volumes on its organometallic chemistry since 1974, with eleven volumes on ferrocenes alone!
  • Uranium has special volumes on nuclear fuel behavior, extraction and purification.
  • Under oxygen: water desalination

Choice of Primary Element

• Gmelin uses its own Principle of Latest Entry. Whichever is the "latest" element in the compound is one chosen.
• The general order of preference is:
  • "Noble gases": He, Ne, Ar, Kr, Rn in one volume.
  • Hydrogen
  • Oxygen
  • Nitrogen (except ammonium compounds, see below, between K and Rb)
  • Halogens: F, Cl, Br, I, At
  • Group VIA: S, Se, Te, Po
  • Group VA: P, As, Sb, Bi
  • Boron
  • Silicon
  • Group IA: Li, Na, K, NH4+, Rb, Cs, Fr
  • Group IIA: Be, Mg, Ca, Sr, Ba, Ra and IIB: Zn, Cd, Hg
  • Group IIIA: Al, Ga, In, Tl
  • Sc, Y, Lanthanides
  • Group IVA: Ge, Sn, Pb and Group IVB: Ti, Zr, Hf plus Th
  • Group VB: V, Nb, Ta, plus Pa
  • Group VIB: Cr, Mo, W, plus U
  • Mn
  • Group VIII: Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt
  • Group IB: Cu, Ag, Au
  • Tc, Re, transuranics
• Volume Examples:
  • NaCl -- Sodium is Vol. 21; Chlorine is Vol. 6. Therefore, Vol. 21
  • Ferrocene - Carbon is Vol. 14; Hydrogen is Vol. 2; Iron is Vol. 59. Therefore Ferrocene appears in Vol. 59
  • (NH4)2Cr2O7 -- Chromium is Vol 52; Ammonium gets its own volume, 23: Oxygen is Vol. 2. Therefore: Vol. 52.

Indexing in Gmelin

• Gmelin has comprehensive formula indexes, in three parts: 1924-74, 1974-79, and 1980-87. The index for 1988-1992 is now being published.
• Formulas are listed alphabetically using an inverted form of Hill notation
  • If no carbon is present, all elements in alphabetical order: e.g. ClNa, H2O4S
  • If carbon is present, then all other elements first, followed by carbon and hydrogen if any.

© 2012 Charles F. Huber

This work by Charles F. Huber is licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License.
Based on a work at guides.library.ucsb.edu