The long and winding road to chemical information

The Long and Winding Road toChemical Information

Engelbert Zass (retd.)

Chemistry Biology PharmacyInformation Center

ETH Zurich

8093 Zürich, Switzerland

Dedicated to the Memory of

© E. Zass, 8th German Conf. on Chemoinformatics, Goslar, 12.11.2012 2

Dr. Ursula Schoch-Grübler Prof. Dr. Reiner Luckenbach1949 – 2011 1941 – 2011

Beilstein ⇒ Reaxys


Beilstein: Handbook ⇐ Excerption


Beilstein: Handbook ⇒ Database




1994

2009

1988

1991





The Long and Winding Road to

Chemical Information




Robert Burns

Woodward

1917-1979




330 publications,including 100 patents

3rd Europ. Symp. Vitamin B12 and Intrinsic Factor

Zürich, March 1979


Vitamin B12

Total Synthesis:

R.B. Woodward




Heterocycles 82, 63-86 (2010)

Publications by A. Eschenmoser




SciFinder: Molecular Formula

• Manganese(II)sulfate

MnO4S ⇒ H2O4S . Mn

• Iron(II)formiate

CHFeO2 ⇒ CH2O2 . ½ Fe

• Berylliumphosphate

Be3O8P2 ⇒ Be . 2/3 H3O4P

but:

• Sodium ClorideCl Na (Cl . Na gives different result)



Ca3(PO4)2 • 3 H2O

SciFinder: Claims and Hype


Essentially correct and true (relatively speaking)

Hype and dangerous insinuation !

SciFinder: Preparation of a Compound

• Search via:

1. Get Reaction: Product

(CASREACT)

2. Additional Reactions

(CASREACT ⇒ CAplus)

3. Registry Role Matrix (Patents, Nonpatents)

(Registry ⇒ CAplus)

4. Get References – Limit results to: Preparation

(CAplus)


© E. Zass, 8th German Conf. on Chemoinformatics, Goslar, 12.11.2012

Preparation of Lidocaine (27.6.2009)

• Reaxys

23 refs. 1946-2008

• SciFinder Web

– CASREACT: 4 refs. 1984-2009

– CAplus: 109 refs. 1948-2009

only 45 relevant !

CHMINF-L


Steroids with Data in Literature


all carbon skeleton, any bonds, any substitution, no anellated rings

Properties: Data, Spectra


SciFinder:

Dipole Moments for

Aminoquinolines



Reaxys:

Dipole Moments for

Aminoquinolines

Dipole Moments of

Aminoquinolines and Aminoacridines



cis-Hydroxylation: SciFinder / Reaxys

Reagenz Reaxys SciFinder

H2O2 / Molybdenum tungsten hydroxide oxide phosphate 7

H2O2 / Tricarbonyl(η5-cyclopentadienyl)(phenylethynyl)molybdenum 1

H2O2 / fac-Trichloro(1,4,7-trimethyl-1,4,7-triazacyclononane)ruthenium 1

H2O2 / Ruthenium(1+), aqua(octahydro-1,4,7-trimethyl-1H-1,4,7-triazonine-

κN1,κN4,κN7)bis(2,2,2-trifluoroacetato-κO)-, (OC-6-33)-, 2,2,2-trifluoroacetate (1:1)

1 3

H2O2 1 1

B2Cl4 / H2O2 1

H2O2 / Tris-µ-oxobis[(1,4,7-trimethyl-1,4,7-triazacyclononane)manganese(IV)]

hexafluorophosphate

1 1

KMnO4 10 1

Methyltriphenylphosphonium permanganate 1

N-methylmorpholineoxide / OsO4 1 2

K2OsO4 / OsO4 1

K3Fe(CN)6 / K2OsO4 1 1

I2 / AgOAc 1 1

cis-Hydroxylation: SciFinder



Chemical Information: State of the Art

• Neither «new» nor «old» sources arecomprehensible or reliable enoughon an individual basis

⇒ one source is usually not enough !

• The traditional strenght of «old» sourcesis partially negated by the complexity oftheir content (data structure)

⇒ improve databases (not only interfaces)

Improve Education & Support


The Past: "Must Use" Brands


Present: Many "Equal" Brands

41© E. Zass, 8th German Conf. on Chemoinformatics, Goslar, 12.11.2012


Dendrobine Total Syntheses (4/2012)

• Total relevant references: 43 (1965-2012)

– SciFinder 38 of 54 (10 excl.)

– Reaxys 13 of 14 (none excl.)

– Web of Knowledge 20 of 22 (none excl.)

– Scopus 18 of 19 (none excl.)

– Google Scholar 18 of 18 (1 excl.: grant)


Databases: Problems and Dangers

2°Literature (A&I, Handbooks) =endangered species ?

• (Relatively) complex interfaces

• Too many sources needed

• Too many differences between sources

• Problematic legacies


(Cost) Effort / Utility ratio not obvious enough


Remedies

• To Producers & Specialists:

– Meta Data about Sources

– Exchange & Feedback of Experience

• To Users:

– Support

– Education & Training



Meta Data: Gmelin, CASREACT







Science

The long and winding road to chemical information