THE BEILSTEIN HANDBOOK OF ORGANIC CHEMISTRY FOR THE OCCASIONAL

USER

 

 

     The Beilstein Handbook of Organic Chemistry is a massive

collection of data on the properties, preparation, and reactions of

carbon compounds.  It covers the literature from the beginning of

organic chemistry early in the 19th century.  Unlike Chemical

Abstracts which tries to publish everything in chemistry, Beilstein

is selective.  The editors have published only critically reviewed

data.

 

     Friedrich Beilstein, a Russian chemist, published the first

edition of his handbook in 1881.  A second edition (1885) and third

edition (1906) were later published.  Each of these editions

covered all the literature published to that time.  These first

three editions are of historical interest only.  They are not used

by chemists today.

 

     In 1918 the fourth edition was published.  It covers the

literature from the beginning of organic chemistry until 1909.  By

this time organic chemistry was growing so rapidly that it was

difficult to keep publishing new editions.  Instead, supplements to

this fourth edition were published.  The following table shows the

basic organization of the fourth edition of the Beilstein Handbook.

 

 

                 BEILSTEIN HANDBOOK ORGANIZATION

 

 

Label   Series Name           Abbreviation   Literature

Color                                        Coverage

 

 

Green   Basic Series             H           up to 1909

        (Hauptwerk)

 

Red     First Supplement         E1 or I     1910 - 1919

        Erstes Erganzungswerk

 

 

White   Second Supplement        EII         1920 - 1929

        Zweites Erganzungswerk

 

 

Blue    Third Supplement         EIII        1930 - 1949

        Drittes Erganzungswerk

        (Volumes 1 - 16)

 

 

Black   Fourth Supplement        EIV         1950 - 1959

        Viertes Erganzungswerk

 

 

Blue +  Combined Third and       EIII & EIV  1930 - 1959

Black   Fourth Supplements

        (Volumes 17-27)

 

 

Red     Fifth Supplement         EV          1960 - 1979

        (In English)

 

 

     Since the basic series and the first four supplements are

totally in German, you may find these abbreviations useful.

 

Auflage = edition.  This is the fourth edition (vierte auflage) of

          Beilstein.

Bindung = Volume

Dritter, Drittes = third

Erster, Erstes = first

Funfter = fifth

Seite (abbreviation s.) = page

Teil = part, or subvolume

Vierter, Viertes = fourth

Zweiter, Zweites = second

 

     Any particular volume in the supplementary series always

contains the same compounds as the volume in the basic series

with the same number.

 

     Volumes 17-27 cover heterocyclic compounds.  World War II

interrupted publication of these volumes, so the third and fourth

supplements were combined for these volumes.

 

     In the basic series, and first and second supplements, each

volume is in one book.  In the later supplements each volume

consists of more that one book, that is each volume is divided into

subvolumes or parts (teil in German).

 

     Even though Beilstein is published in German, you can still

use it without having a reading knowledge of German, because the

editors have used only a limited number of words.  The following

world wide web sites have German-English, and English German dict-

ionaries which contain nearly all the words you will need to know:

    http://www-sul.stanford.edu/depts/swain/beilstein/bedict1.html

    http://www.indiana.edu/~cheminfo/tab10-05.html

    http://www.indiana.edu/~cheminfo/tab11-01.html

 

     Literature references are given for all data.  The basic

series and first four supplements contain a key to the journal

title abbreviations they use.  The fifth supplement uses the

currently accepted standard journal abbreviations.  Many

libraries have a guide to these standard abbreviations:

"Chemical Abstracts Service Source Index (CASSI)".

 

     All entries in the Beilstein Handbook are fully documented.

This means that for every compound in Beilstein, the original

literature source is given for all reactions, preparations, and

every physical data entry.

 

     Sometimes it appears that some literature references are

incomplete.  They are not.  The editors of the Handbook have

always tried to save as much space as possible.  You will see

that they mercilessly abbreviate the titles of journals,

sometimes using just a single letter to denote the title of a

journal with a long name.  The also avoid unnecessary repetition.

 

     Often, the same literature reference is used for more than

one piece of data in a compound.  Instead of repeating the entire

reference, they only give a brief indication of the author or

authors of the reference.  When you see such an entry, look

upwards to see the full reference.

 

     Here is an typical example - the entry for 1-Methyl

cyclohexanol in the fourth supplement (Viertes Erganzungs-

werk), Volume (Band) 6, Part (Teil) 1, page 95.  The

literature reference for the melting point is:

Rocek, Collect. 23 [1958] 833, 834.  The next line has an

entry for the boiling point and the literature reference only

says (Ro.).  In the next paragraph one of the references for

this substances preparation also has as its literature

reference the same brief (Ro.).  By looking upwards from these

two brief entries you will see that they are referring to the

work by Rocek. 

 

 

 

          LOCATING COMPOUNDS IN THE BEILSTEIN HANDBOOK

 

     There are two ways to locate compounds in the Beilstein

Handbook.  You can use the system originally formulated by

Beilstein, where using specific rules you analyze a compound's

structure to determine where it is located in the handbook.  While

experienced users of Beilstein have no trouble applying these

rules, the occasional user can get bogged down here.

 

     Fortunately the editors of the handbook realized that people

do have trouble with the Beilstein system, and they have developed

an easy to use personal computer program to help you find where

compounds are located in the printed handbook.  This program called

SANDRA stands for Structure and Reference Analyser.  You use a

mouse to draw the structure of a compound on your computer monitor,

and the program will tell you where the compound is located in the

handbook.

 

 

                       OBTAINING SANDRA

 

     For several years SANDRA was available free from Beilstein.

It was no longer being updated or supported by Beilstein, and

only a DOS version was available.  You used to be able to obtain

your own copy from the from the Beilstein File Transfer Protocol

(FTP) site as follows:

 

While signed on to the world wide web, type the following in the

location box:

 

ftp://ftp.beilstein.com

   click on:   pub/

      click on:   sandra/

         click on:  sandra.zip

SANDRA would then download as a compressed file (sandra.zip).

 

Sandra.zip needs to be decompressed (unzipped) before you can use

it.  The software to decompress zipped files, pkunzip, is widely

available on the world wide web.  Some sites that currently have

pkunzip and instructions for using it are:

     http://www.shareware.com

     http://pkunzip.com

     http://www.eurekais.com/brock/aazip.htm

 

Alternately, any of the widely available search engines should

always be able to locate sites having pkunzip.

 

After you decompress sandra.zip, the READ.ME file provides all

necessary instructions for using SANDRA.

 

 

If you want a copy of SANDRA, please contact the author of this

tutorial, Philip Barnett, at: phibarn AT-SIGN sci.ccny.cuny.edu

and I will e-mail you a copy of this zipped file.

 

 

 

                      INSTALLING SANDRA

 

     On a DOS based computer, you need to copy all the unzipped

files into a directory, most conveniently named SANDRA.

 

     On a Windows based computer, you can install the unzipped

files and create an icon just as you would for any software

installation.  Some installations of Windows XP may not be able

to run SANDRA.  No problems have been reported with older versions

of Windows.

 

 

                     LIMITATIONS OF SANDRA

 

     Please note that a search in SANDRA will always list a

location in the handbook where that compound should be.  But not

every organic compound is in Beilstein.  Sometimes you will go to

the indicated pages of the handbook and not find your compound in

the basic series or in any of the supplementary volumes.  Sometimes

you will find the compound only in the basic series, or only in one

or two of the supplementary volumes.

 

 

              RESULTS OF A SAMPLE SEARCH IN SANDRA

 

     If you wanted to find benzene in the handbook, you would draw

the structure of benzene on your monitor (later you will see how to

do this) and the result would look like this:

 

     Note that in these structures, / | - and \ represent single

bonds, and // || and \\ represent double bonds.  On the SANDRA

screen, bonds appear as solid lines.  Since this document is in the

simplified ASCII format that cannot show graphics we cannot show

bonds as solid lines.

 

 

H-PAGE 173 to 280    Syst-No 463 to 465

STAMMVERBINDUNG ,  2N-6,  C :  6

 

 

                       C

                     /  \\

                   /      \\

                  C         C

                  ||        |

                  ||        |

                  C         C

                   \      //

                     \  //

                       C

 

------------------------------------------------------------------

E IV subvolume(s) :  5/2                                  C 6 H 6

E III subvolume(s) : 5/2

 

 

                     WHAT THIS SCREEN MEANS

 

     First look at the bottom of the screen.  This tells you that

benzene is found in volume 5 subvolume 2 in both the third and

fourth supplements.

 

     You always want to try to locate your compound in the highest

numbered supplement because if you find the compound there, its

exact page numbers in the earlier supplements and in the basic

series will always be indicated.

 

     The easiest way to locate your compound is by using the

molecular formula which appears at the bottom of the screen.  To

find what page benzene is on, look in the formula index at the back

of subvolume 2 of volume 5.  For benzene you will see it listed

under C 6 H 6.

 

 

WHAT TO DO IF YOU CANNOT FIND THE FORMULA IN THE FORMULA INDEX.

 

     Occasionally your compound may be in Beilstein, but it is not

in the formula index at the back of the subvolume.  Many salts and

complexes of compounds are not listed in the formula indexes.

You can use the other information on the screen to find the

compound.

 

     Note that the second line of the output says 2N-6,  C :  6.

If you go to the table of contents of volume 5 subvolume 2 in the

third or fourth supplements or the table of contents of volume 5 in

the main series or the first or second supplements you will see an

entry for C n H 2n-6.  You will easily find benzene here.

 

     From the Fourth Supplement Table of Contents; volume 5, part 2

 

     Kohlenwasserstoffe C n H 2n-6

     Kohlenwasserstoffe C 6 H 6

               Benzol ............................. 583

 

 

     Another way to locate benzene in one of these subvolumes is to

note the Beilstein System Number (Syst-No) which is displayed at

the top of the screen.  You can browse the subvolume in this range

of system numbers until you find the compound.  Sometimes the

System Number range covers many pages, and you will have to look a

lot.

 

     Now look at the top of the screen.  H-PAGE 173 to 280 gives

you a range of page numbers where benzene is found in the basic

series.

 

     A more complicated example is the following.  If you are

trying to locate the aluminum salt of 8-hydroxyquinoline (a laser

dye) you would draw this structure and ask SANDRA to locate it.

SANDRA would give you the following answer:

 

H-PAGE 77 to 104    Syst-No 3114

Hydroxy (0 : 1 )  2n-11   C : 9

 

 

        C         C                         C         C

      /  \\     /  \\                     /  \\     /  \\

    /      \\ /      \\                 /      \\ /      \\

   C         C         C               C         C         C

   ||        |         |               ||        |         |

   ||        |         |               ||        |         |

   C         C         C               C         C         C

    \      // \      //                 \      // \      //

      \  //     \  //                     \  //     \  //

        N         C                         C         N

                   \                       /

                     \                   /

                       O               O

                         \          /

                           \     /

                             Al

                             |

                             |

                             O

                             |

                             |

                             C         N

                           /  \\     /  \\

                         /      \\ /      \\

                        C         C         C

                        ||        |         |

                        ||        |         |

                        C         C         C

                         \      // \      //

                           \  //     \  //

                             C         C

 

 

-------------------------------------------------------------------

E III/IV subvolume(s) :  21/2                  C 27 H 18 Al N 3 O 3

 

 

     This formula is not in the formula index at the back of this

third and fourth supplementary subvolume of volume 21.  Yet this

compound is in the Beilstein Handbook!

 

     To find this compound in Beilstein you can look in this volume

under this system number (Syst-No 3114). You will find hundreds of

pages with this system number.  To help you find this compound

within these pages you can use the information at the top of the

SANDRA output:

 

               Hydroxy (0 : 1 )  2n-11   C : 9

 

Now look at the Table of Contents at the beginning of this subvolume.

 

From the Table of Contents of Volume 21 Part 2 of the Third and

Fourth Supplement:

 

   Monohydroxy-Verbindungen C n H 2n-11 N O ............. 1057

       Hydroxy-Verbindungen C 9 H 7 N O ................. 1057

       Hydroxy-Verbindungen C 10 H 9 N O ................ 1216

 

 

     Compounds having nine carbons and the general formula 2n-11

begin on page 1057.  You will find this compound on page 1144 in

this subvolume of the third and fourth supplement.  It is listed as

a salt of 8-hydroxyquinoline (molecular formula C 9 H 7 N O), which

is called Chinolin-8-ol in Beilstein.

 

 

                HOW TO DRAW STRUCTURES IN SANDRA

 

On Windows based computers, click on the SANDRA icon you created

when you installed The unzipped files.

The SANDRA screen will then appear.  Press any key to continue.

 

     On DOS based computers you must first type in a few commands.

     On most DOS based computers the mouse is activated when you

     turn on the computer.  If it is not, you must first type

     these two commands:

     C: cd\mouse (enter)

     C: mouse (enter)

     Activate SANDRA by typing the following two commands:

     C: cd\sandra (enter)

     C: sandra (enter)

     The SANDRA screen will then appear.  Press any key to

     continue.

 

 

You will see an arrow in the middle of the screen.  Notice how you

can move the arrow by moving the mouse.

 

In SANDRA there are several ways to draw compounds.  The easiest

way is to draw the compounds atom by atom like you do on paper.

This is the way that is shown here.

 

If you are going to use SANDRA often, there are guides to many

commonly used functional groups and rings.  At the bottom of the

SANDRA screen you will see three boxes:

"PREDEFINED FRAGMENTS", "HELP COMMANDS", and "HELP FRAGMENTS".

You can access these guides by moving the arrow over one of these

boxes and clicking the right hand mouse button.

 

 

Shown here are the directions for drawing a compound that shows all

the challenges you will encounter in drawing structures in SANDRA.

 

                        1-naphthoic acid.

 

 

             7         1            11        12

 

             C         C ---------- C --------OH

           // \      /  \\          ||

         //     \  /      \\        ||

     8  C         C 2     6 C       ||

        |         ||        |       O   13

        |         ||        |

     9  C         C 3     5 C

         \\     /  \      //

           \\ /      \  //

             C         C

 

            10         4

 

The numbers in the structure are the order in which we are going to

draw the atoms.  These numbers do not correspond to any official

numbering system.  Do not worry if you cannot draw the structure

neatly.  SANDRA is not affected if any ring structures you draw are

twisted and oddly shaped.  SANDRA is unaffected if you draw some

bonds long and others short.

 

You must remember three rules when drawing structures:

 

     1- You do not have to draw any hydrogen atoms.  SANDRA

     automatically adds them.

 

     2- Draw all atoms as carbon atoms, and change any non-carbon

     atoms AFTER you have drawn the structure.  There are other

     ways to draw non-carbon atoms, but this is the easiest way.

 

     3- Draw double and triple bonds WHILE your are drawing the

        structure.

 

The mouse has a left hand button which we will call LHB, and a

right hand button which we will call RHB.

 

When you draw structures, you will be asked to either "click LHB"

or "click RHB".  This means that you briefly press then release

that mouse button.  Do not hold the button down.

 

Start with the arrow near the top and center of the screen.

 

Click LHB, and notice that the arrow disappears.  You can now start

drawing the structure.  Move the mouse toward you and to your left

about one inch.  You have now drawn the first two atoms of the

structure.  Click LHB.

 

                    /

                  /

                /

 

 

Move the mouse to make a vertical line down the screen about one

inch long.  Note that we wish to make this bond a double bond.

Press the number 2 key, and notice how a double bond appears on the

screen.  Click LHB.

 

                    /

                  /

                /

               ||

               ||

               ||

 

 

Move the mouse down and towards your right about one inch, press

the number 1 key to bring SANDRA back to drawing single bonds.

Click LHB.  You have now drawn atoms 1 - 4 of the structure.

 

                   /

                 /

               /

              ||

              ||

              ||

               \

                 \

                   \

 

 

Move the mouse up and towards your right about one inch, press the

number 2 key then click LHB.

 

                    /

                  /

                /

               ||

               ||

               ||

                \         //

                  \     //

                    \ //

 

 

Move the mouse to make a vertical line about one inch long, press

the number 1 key, then click LHB.

 

                    /

                  /

                /

               ||          |

               ||          |

               ||          |

                \         //

                  \     //

                    \ //

 

 

Move the mouse back to the starting point, press the number 2 key,

then click LHB.  Click LHB again to release the cursor.  You will

now see the arrow key, and you can move it anywhere on the screen

without drawing any atoms.

 

 

                    / \\

                  /     \\

                /         \\

               ||          |

               ||          |

               ||          |

                \         //

                  \     //

                    \ //

 

Press the S key, and all the carbon atoms will now be visible.

 

                    1

 

                    C

                  /  \\

                /      \\

               C  2      C  6

               ||        |

               ||        |

               C  3      C  5

                \      //

                  \  //

                    C

 

                    4

 

 

You can now draw the second ring containing atoms 7,8,9 and 10.

Bring the arrow directly over atom 2, click LHB.  Move the mouse up

and towards your left about one inch, press the number 1 key to

reset drawing single bonds, click LHB.

 

             7         1

 

             C         C

              \      /  \\

                \  /      \\

                  C 2     6 C

                  ||        |

                  ||        |

                  C 3     5 C

                   \      //

                     \  //

                       C

 

                       4

 

 

Move the mouse down and towards your left about one inch, press the

number 2 key, then click LHB.

 

             7         1

 

             C         C

           // \      /  \\

         //     \  /      \\

     8  C         C 2     6 C

                  ||        |

                  ||        |

                  C 3     5 C

                   \      //

                     \  //

                       C

 

                       4

 

 

Draw a vertical line on the screen about one inch long, press the

number 1 key, and then click LHB.

 

             7         1

 

             C         C

           // \      /  \\

         //     \  /      \\

     8  C         C 2     6 C

        |         ||        |

        |         ||        |

     9  C         C 3     5 C

                   \      //

                     \  //

                       C

 

                       4

 

 

Move the mouse down and towards you about one inch, press the

number 2 key then click LHB.

 

             7         1

 

             C         C

           // \      /  \\

         //     \  /      \\

     8  C         C 2     6 C

        |         ||        |

        |         ||        |

     9  C         C 3     5 C

         \\        \      //

           \\        \  //

             C         C

 

            10         4

 

 

Move the mouse directly over atom 3, press the number 1 key, click

LHB, then click LHB again to release the arrow.

 

             7         1

 

             C         C

           // \      /  \\

         //     \  /      \\

     8  C         C 2     6 C

        |         ||        |

        |         ||        |

     9  C         C 3     5 C

         \\     /  \      //

           \\ /      \  //

             C         C

 

            10         4

 

 

DON'T WORRY IF THERE ARE MISTAKES, SUCH AS EXTRA ATOMS OR THE WRONG

KIND OF BONDS IN THE STRUCTURE.  LATER YOU WILL SEE HOW TO CORRECT

MISTAKES WITHOUT HAVING TO REDRAW THE ENTIRE STRUCTURE.

 

You are now ready to draw the carboxylic acid group.  Move the

arrow directly over atom 1, click LHB.  Move the mouse about one

inch to the right, click LHB.  You have now drawn the carbon of the

carboxylic acid. Again move the mouse about one inch to the right,

then click LHB twice.

 

             7         1            11       12

 

             C         C ---------- C --------C

           // \      /  \\

         //     \  /      \\

     8  C         C 2     6 C

        |         ||        |

        |         ||        |

     9  C         C 3     5 C

         \\     /  \      //

           \\ /      \  //

             C         C

 

            10         4

 

 

Move the arrow directly over the carboxylic acid carbon (atom

number 11).  Click LHB draw a vertical line down, press the number

2 key, click LHB twice.

 

             7         1            11       12

 

             C         C ---------- C --------C

           // \      /  \\          ||

         //     \  /      \\        ||

     8  C         C 2     6 C       ||

        |         ||        |       C  13

        |         ||        |

     9  C         C 3     5 C

         \\     /  \      //

           \\ /      \  //

             C         C

 

            10         4

 

You have now drawn all the atoms you need to draw.  Remember, you

do not have to draw any hydrogen atoms.

 

You are now ready to change atoms 12 and 13 to oxygen atoms.

 

Move the arrow directly over atom 12, click LHB, now without moving

the mouse, type the letter O and then press the ENTER key.  Click

LHB twice.

 

             7         1            11       12

 

             C         C ---------- C --------O

           // \      /  \\          ||

         //     \  /      \\        ||

     8  C         C 2     6 C       ||

        |         ||        |       C   13

        |         ||        |

     9  C         C 3     5 C

         \\     /  \      //

           \\ /      \  //

             C         C

 

            10         4

 

 

Move the arrow directly over atom 13 and repeat what you just did

for atom 12.

 

             7         1            11       12

 

             C         C ---------- C --------O

           // \      /  \\          ||

         //     \  /      \\        ||

     8  C         C 2     6 C       ||

        |         ||        |       O   13

        |         ||        |

     9  C         C 3     5 C

         \\     /  \      //

           \\ /      \  //

             C         C

 

            10         4

 

 

The structure is now complete, and the arrow appears on the screen.

 

press the Q key.  SANDRA will now give you the answer.

 

SANDRA will now ask you if you want another molecule.

 

If you press N you will exit SANDRA.

 

If you press Y, SANDRA will recall the last structure.  You can

either reuse this structure, or you can press the letter K (for

kill!) then the letter Y to clear the screen, and you are now

ready to draw a new structure.

 

 

 

                       CORRECTING MISTAKES

 

 

If you make a mistake in drawing the structure, you do not have to

begin again.  You can correct the mistakes in what you drew.

 

For example, you wanted to draw benzene, but instead drew the

following:

                    1

 

                    C

                  //  \

                 //    C 7

                //      \

            2  C         C 6

               |        ||

               |        ||

            3  C         C 5

                \       /

                  \   /

                    C

 

                    4

 

You accidentally drew an extra carbon, and you forgot to draw a

double bond between atoms 3 and 4.

 

To erase the extra carbon (C7), move the arrow directly over C7,

then click RHB twice.  You will see the following:

 

                    1

 

                    C

                  //

                 //

                //

            2  C         C 6

               |        ||

               |        ||

            3  C         C 5

                \       /

                  \   /

                    C

 

                    4

 

Now place the arrow directly over C6, click LHB, draw a line that

ends directly over C1, click LHB twice.  You now have:

 

                    1

 

                    C

                  // \

                //     \

            2  C         C 6

               |        ||

               |        ||

            3  C         C 5

                \       /

                  \   /

                    C

 

                    4

 

You are now ready to draw the double bond between carbons 3 and 4.

But first you must remove C3.  Move the arrow directly over C3,

click RHB twice.  You now have:

 

                    1

 

                    C

                  // \

                //     \

            2  C         C 6

                        ||

                        ||

                         C 5

                        /

                      /

                    C

 

                    4

 

Move the arrow directly over C2, click LHB, draw a vertical line,

click LHB, draw a line that ends directly over C4, press the number

2, click LHB twice.  You now have the structure of benzene.

 

                    1

 

                    C

                  // \

                //     \

            2  C         C 6

               |        ||

               |        ||

            3  C         C 5

                \\      /

                  \\  /

                    C

 

                    4

 

 

 

                                         Philip Barnett

                                         City College of New York

                                         Science/Engineering Library

                                         June 1995

                                         Updated: August 1999

                                         Expanded and Updated: December 2004

CCIIM: 33-16.695