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Home   •   Support and Training  •  SciFinder  •  Strategies  •  Controlling Substitution
Controlling Substitution
Introduction This topic identifies techniques for controlling substitution in substructure search results.
Definition Substructure searching retrieves matches of a structural skeleton with substitution at "open positions."  An open position occurs when an atom contains fewer than the maximum number of allowed bonds, based on the valency of the atom.
Illustration

This structure has two open positions at the middle carbon (standard valence of carbon is four):

Controlling Substitution 1 

Default retrieval possibilities

By default, a substructure search on the above structure retrieves the following:

Substituted structure matches with

Example

Bonds at open positions
Controlling Substitution 2
Controlling Substitution 5
Controlling Substitution 6
Controlling Substitution 7
An electron at an open position (radical)

Controlling Substitution 8

Note: The single electron is not drawn in the structure.

A pair of electrons (-) or no electrons (+) at an open position
Controlling Substitution 9

 

 

 

 

 

 

 

 

 

 

 

 

 

Tools to control substitution

Tools and structure drawing techniques are available to control substitution:

  • Variables menu
  • R-group tool
  • Lock Atoms tool
  • Drawing hydrogen attachments

 

Variables menu and R-group tool

The Variables menu and R-group tool control substitution by specifying substituents at open positions.

  • The Variables menu  wvariable.jpg contains a list of predefined variable symbols, e.g., X = all halogen atoms.
  • The R-group tool wrgroup.jpg is used to create customized variable groups containing combinations of atoms, shortcuts, and variables.

Lock Atoms tool

The Lock Atoms tool wlock.jpg locks an open position from substitution. It prevents retrieval of structures having a bond to a non-hydrogen atom at an open position.

Using the Lock Atoms tool on the middle carbon

Retrieves matches

 

Controlling Substitution 15
Without substitution at the open positions on the middle carbon. Matches with a hydrogen attachment, one electron (radicals), two electrons (anions), and no electrons (cations) are allowed.

Controlling Substitution 7a

Controlling Substitution 8a

 

 

 

 

 

 

 

 

 

Drawing hydrogen attachments

Drawing a hydrogen attachment to an open position controls substitution at that position.

Drawing a H attachment on the middle carbon

Retrieves matches

 

Controlling Substitution 4
With substitution at the single, open position on the middle carbon

Controlling Substitution 5a

 

 

 

 

 

 

 

 

Terminal positions

Terminal shortcuts - such as Me - are locked from substitution by default.

To allow substitution at a terminal position, draw the open position explicitly.

If, at a terminal atom, you want

Do this

Example
Substitution Draw the position open

Controlling Substitution 9a

No substitution Use the Lock Atoms tool on the terminal atom 

Controlling Substitution 13 

Limited substitution Use a terminal shortcut

 Controlling Substitution 11

Draw one or more hydrogen attachments to the terminal atom

Controlling Substitution 16 

Updated: 10/5/2009 9:56:50 AM
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