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Transcript of 1 Reaction Searching in STN. 2 Main Files searchable for reactions in STN: Beilstein CASREACT ...
1
Reaction Searching in STN
2
Reaction Searching in STN
Main Files searchable for reactions in STN:
Beilstein CASREACT CheminformRX DJSMOnline PS Registry-CAPlus Synthline
3
CASREACT
4
Overview
• CASREACT is an organic chemical reaction database produced by CAS.
• CASREACT covers chemical reactions from the Organic sections of Caplus.
• CASREACT contains displayable reaction schemes for, single - and multi-step, reactions.
• CASREACT is updated weekly, with >600-1300 new reactions.
5
• >10,000,000 reactions >4,000,000 single-step reactions
>5,000,000 multi-step reactions
• >500,000 source documents>65,500 patents
>341,500 journal articles
Overview
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• From 1907-1985– Partial reactions coverage (InfoChem, INPI)
• From 1985-1991– All reactions in selected articles from a list of 106 journals in the
organic CA sections
• From 1991-2002– Representative reactions from journals and patents in the organic CA
sections
• From 2003– Extended to all reactions from selected articles in the 30 journals,
which are richest in reaction information– Representative reactions from the remaining journal articles and
patents selected for CASREACT coverage
Overview
7
Three File Segments• Original CASREACT reactions
– Synthetically useful organic and organometallic reactions from CA sections 21-34 (1985-1990)
– Coverage expanded to sections 41, 7, and 16 in 1991-
• InfoChem/VINITI reactions– Methods for preparing a variety of organic substances, including
aliphatic, alicyclic, and heterocyclic compounds, natural products, and organometallics. Journals 1974-1991; Patents 1982-1991
• INPI reactions (French Core Reactions Database)– Proven synthetic methods for preparing primarily heterocyclic
compounds, carbohydrates, and steroids. 1907-1985
Overview
8
Journals
1985 Present1974
InfoChem
CAS
Patents
1991
Partial reaction coverage is provided from 1907-1985 via the reactions from InfoChem and INPI that could be algorithmically converted into CASREACT format.
~ ~
1907
INPI~ ~
Present1982 1991
~ ~
1907
~ ~
CAS
INPI
1985
InfoChem
Overview
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• Search terms in CASREACT include:
Structures for reactants/reagents and products in
the same query All reaction participants, most via CAS Registry
Numbers Reaction yields, number of steps, and additional
reaction notes
Overview
10
• CASREACT records contain:
One or more searchable/displayable chemical
reactions All of the information contained in the associated
CAplus record
Overview
11
Sample Record
Bibliographic Information (BIB)
AN 119:49291 CASREACTTI A new synthesis of pyrazolo[3,4-d]thiazolesAU Vicentini, Chiara B.; Veronese, Augusto C.;
Guarneri, Mario; Manfrini, Maurizio; Giori, PaoloCS Dip. Sci. Farm., Univ. Ferrara, Ferrara, 44100,
ItalySO Heterocycles (1993), 36(4), 857-63 CODEN: HTCYAM; ISSN: 0385-5414DT JournalLA EnglishCC 28-7 (Heterocyclic Compounds (More Than One Hetero
Atom))
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Abstract (ABS)
GI
AB An efficient synthesis of pyrazolo[3,4-d]thiazoles I (R = Me, PhCH2, Ph) was achieved by treatment of N-(4-amino-5- pyrazolyl)thiocarboxamides II with sodium nitrite in acidic medium followed by irradn. with UV light.
• All of the BIB and ABS information from CAplus is searchable in CASREACT.
NN N
S
RPh
eM
I NN
NH2
NHCSRPh
eM
II
Sample Record
13
Indexing (IND)
ST pyrazolothiazole; aminopyrazolylthiocarboxamide diazotization photochem cyclizationIT Ring closure and formation (photochem., of aminopyrazolyl)thiocarboxamides to pyrazolothioazoles)IT 23676-92-8 54621-93-1 RL: RCT (Reactant) (nitroso group redn. of)IT 148368-70-1P RL: RCT (Reactant); SPN (Synthetic preparation);
PREP (Preparation) (prepn. and nitroso group redn. of)
o o o
• All of the CAplus indexing information is searchable, except for the CAS RNs.
Sample Record
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RX(1) OF 10 A + B ===> C...
RX(1) RCT A 52943-85-8, B 103-80-0
RGT D 144-55-8 NaHCO3
PRO C 148368-70-1
SOL 67-66-3 CHCl3, 7732-18-5 Water
RX(2) OF 10 ...C ===> G …
o o o
MePh
NONH
NN
H *
A
PhCl
O
*
B(1)
Me
Ph
Ph
NONH
O
NN
*
YIELD 79%C
Map - Letter placeholder for each reactant and product
Diagram - Structures for reactants and products with broken/formed bonds are marked with an asterisk (*)Summary - CAS RNs and Role for each participant
Me
Ph
Ph
NH
O
NN
NO
*
C(2)
Me
Ph
Ph
NH
O
NN
NH
H*
YIELD 87%G
Sample Record
15
RX(5) OF 10 COMPOSED OF RX(1), RX(2)RX(5) A + B ===> G
RX(1) RCT A 52943-85-8, B 103-80-0 RGT D 144-55-8 NaHCO3 PRO C 148368-70-1 SOL 67-66-3 CHCl3, 7732-18-5 Water RX(2) RCT C 148368-70-1 RGT H 7803-57-8 N2H4-H2O PRO G 148368-71-2 CAT 7440-05-3 Pd SOL 67-56-1 MeOH
o o o
MePh
NH
NN
NOH * *
A
PhCl
O
*
B
2 STEPS
Me
Ph
Ph
NH
O
NN
NH
H
*
*
YIELD 87%G
Products from Step 2
Reactants from Step 1
Summary - Step 1
Summary - Step 2
Sample Record
16
CASREACT Coverage
CASREACT covers reactions used to prepare:
Aliphatic compounds Alicyclic compounds Alkaloids, steroids, and carbohydrates Amino acids, peptides, and proteins Benzene and condensed benzene compounds Dyes and organic pigments Heterocyclic compounds Organometallic compounds (compounds with at least one carbon-metal bond)
Terpenes and terpenoids
17
p. 6
CASREACT does NOT cover reactions used to
prepare:
Inorganic compounds Coordination compounds with no carbon-metal bonds Polymers Surfactants and detergents
CASREACT Coverage
18
p. 7
A variety of reaction types:
Straightforward single-step and multi-step synthetic reactions
Stereospecific syntheses Biologically mediated reactions, e.g., enzymatic
conversions "Pot" reactions (multi-step reaction in which intermediates
are not isolated) Failed reactions (if the intent was potentially synthetically
useful)
CASREACT Coverage
19
p. 7
Reactions typically not covered in CASREACT include:
Conventional preparations for physiochemical or pharmacological studies
Conventional methods of isotopic labeling Conventional methods for amino acid or
carbohydrate coupling Reactions of compounds where there is no change
in the atom connections in the reaction
CASREACT Coverage
20
Reaction Search Terms
A variety of search terms can be used in CASREACT to:
Describe a reaction Focus a reaction search Focus a reaction answer set
21
Terms to describe a reaction: Structure diagrams for reactant/reagent and product
A=>? What is made from this reactant?
? => B How is this product made?
A=>B Reactant going to a product
Functional groups appearing in the reactant/reagent and product
Group that is formed in the reaction
Group that reacts
Group that does not participate in the reaction
Reaction Search Terms
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Terms to focus a reaction search: Yield Number of steps CAS RNs for other reaction participants Reaction note
Terms to focus a reaction answer set: Document type Publication year Author Company name
Reaction Search Terms
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Ways for searching In CASREACT
Basic Index
Structures
Functional Groups
24
Basic Index contains:
CAS Registry Numbers forCAS Registry Numbers for:
reagents, solvents, and catalysts
Single words fromSingle words from::
title, supplementary terms, abstract,
index terms,reaction note.
Basic Index
25
=> fil casreact
=> enzym? or biotransform? or yeast
L1 18695 ENZYM? OR BIOTRANSFORM? OR YEAST
=> (enzym? or biotransform? or yeast)/nte
L2 11368 (ENZYM? OR BIOTRANSFORM? OR YEAST)/NTE
=> d hit
L2 ANSWER 1 OF 11368 CASREACT COPYRIGHT 2005 ACS on STN
NTE biotransformation, enzymic, stereoselective,
enantioselective (S-alc. in 99% ee), lipase PS-30
is immobilized on Celite 545
Basic Index
26
Search Question:
Locate methods for converting the following thioamides to the corresponding nitriles:
R1, R2, R3, R4 = Anything, including hydrogen
Structures
27
3. Upload the reaction query
2. Logon to STN and enter CASREACT
1. Build and save the reaction query
Structures
28
5. Display the reactions
4. Run the reaction search
Structures
29
• To build a Reactant => Product reaction query:
A Draw the structure diagramsB Specify the reaction featuresC Save the reaction query
Structures
30
A. Draw the structure diagrams
1. Click on the Prepare Query button on the main STN Express screen to open the structure drawing screen.
2. Draw the structure for the reactant and the structure for the product in the same structure drawing window.
Structures
31
B. Specify the reaction features1. Click on the Reaction button to activate the
reaction feature buttons on the vertical toolbar.To assign a Use the
Reaction direction Reaction Arrow Tool
Fragment role Reaction Role Tool
Bond that is changed/unchanged in the reaction
Reaction Site Tool
Mapping between an atom in the reactant and product
Reaction Mapping Tool
Structures
32
B. Specify the reaction features2. To specify reactant and product, right click the Reaction
Arrow Tool and draw an arrow from the reactant to the product.
Structures
N
33
The role reactant/reagent is assigned to the structure at the beginning of the arrow and the role product is assigned to the structure at the end of the arrow.
NOTE:
The role "reactant/reagent" is assigned instead of "reactant" because a compound may be considered to be a reactant in one paper and a reagent in others.
To maximize the number of reactions retrieved, the broader role of reactant or reagent is assigned to the starting material.
Structures
34
C. Save the reaction query
1. Click the Save button . The Save Query As dialog box appears.
2. In the File Name: entry box, type a name for the query.
Click Save.
Structures
35
C. Save the reaction query3. On the second save screen, click Save.
Structures
36
1. Logon to STN by clicking the Logon button . You are placed in the HOME file on STN.
2. Use the FILE command to enter a reaction database.
* * * * * * * * * * STN Columbus * * * * * * * * * * *
FILE 'HOME' ENTERED AT 16:01:49 ON 16 NOV 2000
=> FILE CASREACT
Structures
37
1. Start the structure uploading process by clicking the Upload Structure Query button .
2. Choose the name of the structure to upload. Click Open.
Structures
N
38
Select the type of database in which you will do the search. Click OK.
NOTE - NOTE - The query will be uploaded as a reaction only in the reaction-The query will be uploaded as a reaction only in the reaction-searchable databases. In the other databases, the reactant and searchable databases. In the other databases, the reactant and product will be uploaded as separate structure queries.product will be uploaded as separate structure queries.
Structures
39
When structure upload is completed, an L-
number is assigned to the structure reaction
query.
=>
Uploading r1.str
L1 STRUCTURE UPLOADED
Structures
40
Option: Verify the reaction query online
Display the uploaded reaction and verify that it
corresponds to the reaction you wish to search.=> D L1
L1 HAS NO ANSWERS
L1 STR
Structure attributes must be viewed using STN Express query preparation.
SN
O
N
O
H
H H
H H
H H
H
Structures
41
The SEARCH command is used to run a reaction search. The command line needs three pieces of information:
1. The L-number of the uploaded reaction query.
2. The type of search you want to perform:
3. The scope of the search:
Type of searchSSS CSS
Allows substitution at any open site in the query
Blocks substitution at any open site in the query
Scope of searchSAM FULL
Search a portion of the database (no cost)
Search the entire database (search fees apply)
Structures
42
Running a reaction search involves three steps:
A. Run a SAMPLE search
B. Evaluate answers
C. Run a FULL search
Structures
43
The SAMPLE search is a no-cost way to:
'Test' your query to make sure it will run within system limits
Verify that the types of answers retrieved are the types of answers you want
Structures
44
=> S L1 SSS SAM
SAMPLE SEARCH INITIATED 14:37:13 FILE 'CASREACT'
SCREENING COMPLETE - 2 REACTIONS TO VERIFY FROM 2 DOCUMENTS
100.0% DONE 2 VERIFIED 1 HIT RXNS 1 DOCS
SEARCH TIME: 00.00.01
FULL FILE PROJECTIONS: ONLINE **COMPLETE**
BATCH **COMPLETE**
PROJECTED VERIFICATIONS: 2 TO 124
PROJECTED ANSWERS: 1 TO 79
L2 1 SEA SSS SAM L1 (1 REACTIONS)
The search is projected to complete in the full database.
Each answer contains one or more reactions that match the query.
Each answer is a document record.
Structures
45
In CASREACT the no-cost D SCAN feature shows the:
Title of the publication First hit reaction in a condensed form
=> D SCAN
L2 1 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Nitrile-formamide chloride adducts. X. Formation of nitriles by base-induced fragmentation of N- acylamides and their heteroanalogous derivatives
ALL ANSWERS HAVE BEEN SCANNED
RX(2) OF 5
NMe2
MeO
C N
S
CH
MeO
CN
32%
NaOH, Water
Structures
46
=> S L1 SSS FULL
FULL SEARCH INITIATED 14:37:49 FILE 'CASREACT'
SCREENING COMPLETE - 24 REACTIONS TO VERIFY FROM 15 DOCUMENTS
100.0% DONE 24 VERIFIED 9 HIT RXNS 7 DOCS
SEARCH TIME: 00.00.02
L3 7 SEA SSS FUL L1 (9 REACTIONS)
=> D SCAN
L3 7 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Mild and selective oxidations with polystyrene- bound diaryl selenoxide
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1
RX(20) OF 27
MeO
C NH2
S
MeO
PhSe
O
+MeO
CNEtOH
NOTE: Polymer-bound selenoxide
D SCAN randomly selects answers from the answer set for display.
The FULL search retrieved 7 documents containing a total of 9 reactions that match the query.
Structures
47
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1
L3 7 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI A new, efficient one-pot preparation of nitriles from thiocarboxamides
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):0
RX(1) OF 4
MeO
C NH2
S
(step 1)
MeO
CN
70%
1. Me2N:CHO2SCl.Cl, CH2Cl22. Pyridine, CH2Cl2
Type "0" or "END" to exit from D SCAN.
Structures
48
Many display formats are available in CASREACT to
view additional information from an answer. To use
the display formats with the DISPLAY command,
enter in any order:
Format name L-number of the answer set Answer numbers
Example:To display answers 1-7 from L3 in the FHIT format, enter
=> D L3 1-7 FHIT=> D L3 1-7 FHIT
Structures
49
Use this format To display
OCC The number of hit reactions in each answer
CRD All hit reactions for each answer in the compact format
FCRDREF (default) First hit reaction for each answer in the compact format,plus the reference
CRDREF All hit reactions for each answer in the compact format, plusthe reference
FHIT First hit reaction for each answer in the full format (Map,Diagram, and Summary - includes CAS RNs for eachparticipant)
HIT All hit reactions for each answer in the full format (Map,Diagram, and Summary - includes CAS RNs for eachparticipant)
BIB Full bibliographic information
ABS Abstract from printed Chemical Abstracts
Structures
50
=> D L3 1-4 OCC L3 ANSWER 1 OF 7 CASREACT COPYRIGHT 2000 ACSNUMBER OF HIT REACTIONS 2NUMBER OF REACTIONS IN PATH 2NUMBER OF REACTIONS IN SPATH 2FIELD COUNTRX(4) 2 RX(5) 2 L3 ANSWER 2 OF 7 CASREACT COPYRIGHT 1998 ACSNUMBER OF HIT REACTIONS 1NUMBER OF REACTIONS IN PATH 1NUMBER OF REACTIONS IN SPATH 1FIELD COUNTRX(1) 2 o o o
OCC displays information about the "hits" in the answer. The first line shows the number of reactions that matched the search query.
Structures
51
=> D L3 1 CRD
L3 ANSWER 1 OF 7 CASREACT COPYRIGHT 2000 ACS
RX(4) OF 9
MeO
C NH2
S
MeO
CN
96%
TeCl4, Et3N, CHCl3
RX(5) OF 9
MeO
C NH2
S
MeO
CN
+
88%
OMeMeO
N
NS
8%
SeCl4, Et3N, CHCl3
CRD shows all hit reactions for an answer.
Structures
52
=> D L3 1 FHIT
L3 ANSWER 1 OF 7 CASREACT COPYRIGHT 2000 ACS
RX(4) OF 9 J ===> K
RX(4) RCT J 2362-64-3
RGT C 10026-07-0 TeCl4, D 121-44-8 Et3N
PRO K 874-90-8
SOL 67-66-3 CHCl3
MeO
NH
S
H**
*
J(4)
MeO
C N*
YIELD 96%K
REACTION SUMMARY
REACTIONMAP
REACTION DETAILS
Structures
53
The FHIT and HIT formats are useful when you need
to see the CAS RNs for one or more of the reaction
participants.
Structures
54
=> D L3 1-3
L3 ANSWER 1 OF 7 CASREACT COPYRIGHT 2000 ACS
L3 ANSWER 2 OF 7 CASREACT COPYRIGHT 2000 ACS
L3 ANSWER 3 OF 7 CASREACT COPYRIGHT 2000 ACS
RX(4) OF 9
MeO
C NH2
S
MeO
CN
96%
TeCl4, Et3N, CHCl3
REF: J. Chem. Res., Synop., (4), 152-3; 1995
RX(1) OF 4
MeO
C NH2
S
(step 1)
MeO
CN
70%
1. Me2N:CHO2SCl.Cl, CH2Cl22. Pyridine, CH2Cl2
REF: Indian J. Chem., Sect. B, 30B(11), 1065-6; 1991
RX(2) OF 5
NMe2
MeO
C N
S
CH
MeO
CN
32%
NaOH, Water
REF: J. Prakt. Chem., 330(5), 847-50; 1988
If a display format is not specified on the command line, STN uses the default format for the database to display the results.
Structures
55
=> D L3 3 CRDREF ABSL3 ANSWER 3 OF 7 CASREACT COPYRIGHT 2000 ACS
GI
AB 4-MeOC6H4CN was obtained by treatment of 4- MeOC6H4CCl:NCH:N+Me2 ClO4- or 4-MeOC6H4CSN:CHNMe2
with base. 4-ClC6H4CN was similarly obtained from the pyrrolinium salt I and 3-morpholino-2-
phenylacrylonitrile from the iminium salt II. 3- Phthalimidopropionitrile was prepd. from N-(3-
phthalimidopropionyl) formamide and MeNHNH2.
C(SMe) NClN+
I-Me
I
ON+NCHPhCClClO4- II
RX(2) OF 5
NMe2
MeO
C N
S
CH
MeO
CN
32%
NaOH, Water
REF: J. Prakt. Chem., 330(5), 847-50; 1988
Structures
56
1. To permanently change the default display format:=> SET FORMAT
ENTER FORMAT NAME OR (?):.MYRXN
ENTER FORMAT DEFINITION OR (?):TI CRDREF
SET COMMAND COMPLETED
2. Permanently change default to new format:=> SET DFORMAT PERM .MYRXN
SET COMMAND COMPLETED
Structures
57
1 What types of products have been formed from the reaction of the following two starting materials?
R1 and R2 may be any ring or chain atom including hydrogen.
R3 may be ring or chain atom except hydrogen.
Skills Practice
58
1 Locate the requested information:
A. Build the query.
B. Test it with a SAMPLE search. Will the search run within system limits in the FULL database?
C. Run the search in the FULL database. How many documents were retrieved? How many total hit reactions were in the documents?
D. Display the Title (TI) and CRDREF information for all of the answers. How many different methods were reported for carrying out the conversion?
Skills Practice
59
=> fil casreact=> Uploading C:\Program Files\stnexp\Queries\w9.str L1 STRUCTURE UPLOADED => dL1 HAS NO ANSWERSL1 STR
C NA N
H
H
H
C CC N N+
Ring, Chain
60
=> l1SAMPLE SEARCH INITIATED 06:38:14SCREENING COMPLETE - 142 REACTIONS TO VERIFY FROM 24 DOCUMENTS 100.0% DONE 142 VERIFIED 21 HIT RXNS 6 DOCSSEARCH TIME: 00.00.01 FULL FILE PROJECTIONS: ONLINE **COMPLETE** BATCH **COMPLETE**PROJECTED VERIFICATIONS: 2126 TO 3554PROJECTED ANSWERS: 6 TO 266 L2 6 SEA SSS SAM L1 ( 21 REACTIONS)
61
=> l1 fullFULL SEARCH INITIATED 06:39:49SCREENING COMPLETE - 2571 REACTIONS TO VERIFY FROM 446 DOCUMENTS 100.0% DONE 2571 VERIFIED 531 HIT RXNS 137 DOCSSEARCH TIME: 00.00.01 L3 137 SEA SSS FUL L1 ( 531 REACTIONS)
=> d fhit
62
Ph
N
N
NNH
HH
* *
A
EtMe
NCC
ON **
F(2)
Me
Ph
NC
NN
N
NH
N
H
*** *
YIELD 70%G
63
Ac AcO
A CNNH
O
NH
H*
**
B
Ph
NCC N
H
**
* *
D
2 STEPS
NH
YIELD 32%E: CM 1
Ph
CN
NCN
N
N
O
H
H
**
* **
* **
*
**
YIELD 32%E: CM 2
64
1 Locate the requested information about the conversion of the following ketoximes to the corresponding ketones:
R = any non-hydrogen ring or chain substituent
Rings may have other rings fused to them
Any substitution at all open sites
Skills Practice
65
1 Locate the requested information:
A. Build the query.
B. Test it with a SAMPLE search. Will the search run within system limits in the FULL database?
C. Run the search in the FULL database. How many documents were retrieved? How many total hit reactions were in the documents?
D. Display the Title (TI) and CRDREF information for all of the answers. How many different methods were reported for carrying out the conversion?
Skills Practice
66
=> fil casreact => Uploading C:\Program Files\stnexp\Queries\w9.strL1 STRUCTURE UPLOADED => d
A
Me N
O H
A
Me O
67
=> l1SAMPLE SEARCH INITIATED 16:50:46SCREENING COMPLETE - 170 REACTIONS TO VERIFY FROM 35 DOCUMENTS 100.0% DONE 170 VERIFIED 10 HIT RXNS 5 DOCSSEARCH TIME: 00.00.01 FULL FILE PROJECTIONS: ONLINE **COMPLETE** BATCH **COMPLETE**PROJECTED VERIFICATIONS: 2618 TO 4182PROJECTED ANSWERS: 5 TO 234 L2 5 SEA SSS SAM L1 ( 10 REACTIONS)
68
=> l1 fullFULL SEARCH INITIATED 16:52:14SCREENING COMPLETE - 3336 REACTIONS TO VERIFY FROM 674 DOCUMENTS 100.0% DONE 3336 VERIFIED 143 HIT RXNS 71 DOCSSEARCH TIME: 00.00.01 L3 71 SEA SSS FUL L1 ( 143 REACTIONS)
69
=> d scan L3 71 ANSWERS CASREACT COPYRIGHT 2004 ACS on STN TI Application of Aryloximes as Solid-Phase Ketone Linkers
RX(11) OF 27
Me
PhO
CN OH
(step 1)
Ac
PhO
95%
1. R:94610-82-9, t-BuOK, DMF2. F3CCO2H, Water, MeOH
70
Precision ToolsLocate methods for converting the primary amine to a nitro group in the following types of compounds:
H2N–R–Cl => O2N–R–Cl
R = any type of carbocyclic ring system, e.g., benzene, cyclopentane, etc.
Any other substitution in addition to that shown in the structure is allowed
Structures
71
3. Test the query with a SAMPLE search
2. Logon to STN, enter CASREACT, and upload the
reaction query.
1. Build and save the reaction query.
Structures
72
• When many reactions of the same type are reported in a paper, generally only synthetically useful or structurally representative reactions are included in CASREACT.
• To maximize the retrieval of papers that may contain the types of transformations in which you are interested, make your structure query as broad as possible.
Structures
73
Use this feature To retrieve
Variable groups(X ,M, A, Q, CY, CB,HY, AK)
Broadly defined groups of atoms
G-group A group of atoms that you specify (up to 20atoms)
Node Characteristicof Ring/Chain onchain atoms
Chain atoms that are parts of a ring or a chain
Bond Characteristicof Ring/Chain onchain bonds
Chain bonds that are in a ring or a chain
Leave the site open Any substitution at a position
Structures
74
Worksheet
Directions: Consider the amine => nitro query on the previous page. Which of the above features would you use to make the query as broad as possible?
HN
CbCl
H
ON
CbCl
O
Structures
75
=> FILE CASREACT
Uploading rx2.str
L1 STRUCTURE UPLOADED
=> D L1
L1 HAS NO ANSWERS
L1 STR
Structure attributes must be viewed using STN Express query preparation.
HN
CbCl
H
ON
CbCl
O
Structures
76
=> S L1 SSS SAM
SAMPLE SEARCH INITIATED 15:20:23 FILE 'CASREACT'
SCREENING COMPLETE - 453 REACTIONS TO VERIFY FROM 113 DOCUMENTS
100.0% DONE 453 VERIFIED 12 HIT RXNS 3 DOCS
SEARCH TIME: 00.00.02
FULL FILE PROJECTIONS: ONLINE **COMPLETE**
BATCH **COMPLETE**
PROJECTED VERIFICATIONS: 7785 TO 10335
PROJECTED ANSWERS: 3 TO 163
L2 3 SEA SSS SAM L1 (12 REACTIONS)
Structures
77
=> D SCAN L2 3 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Preparation of benzimidazole phosphono-amino acids
useful as NMDA Antagonists
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):2
RX(2) OF 3NO2
Cl
NH2+
(step 1)
EtO OEtCH2(step 2)
OEt
OEt
NO2
Cl
NH CH2 P
O
95%
1. (EtO)2P(O)H, H2SO4, Water
Structures
78
L2 3 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Radioiodinated p-iodoclonidine. A high-affinity
probe for the .alpha.2-adrenergic receptor
L2 3 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Synthesis of the new pyrido[1,2-c]benzo-v-
triazinium system via valence bond isomerization
ALL ANSWERS HAVE BEEN SCANNED
RX(12) OF 50O2N
Cl
Cl
NH2
CHO
O2N Cl
ClNH
64%
AcOCHO
RX(9) OF 22NO2
Cl
NH2
(step 1)
NO2Cl
N
76%
1. HCl, NaNO2, Water2. Pyridine
Structures
79
Worksheet
Directions: Look at the reactions retrieved in the SAMPLE search. How many of those reactions are the transformation of interest?
Neither one
Structures
80
6. Run the FULL search.
5. Test the modified query with a SAMPLE search
4. Add precision to the query, using map and site
tools.
Structures
81
Two tools are available for improving the precision of
reaction structure queries.
Use this tool When you need to specify that
Atom mappingAn atom in the reactant is thesame atom in the product
Reaction siteA bond is completelychanged, partially changed, orunchanged in the reaction
Structures
82
Atom MappingTo map atoms in a reaction query:
1. Click on the Atom mapping tool .
2. A mapping-type option box appears.
Select Manual Mapping. Click OK.
Structures
83
To map atoms in a reaction query:
3. Click on an atom in the reactant and the corresponding atom in the product.
Identical numbers indicate mapped atoms.
Structures
Atom Mapping
84
Mapping may NOT be used with
Shortcut symbols Variable groups G-groups Different elements, e.g. you cannot map C to N
Atom Mapping
Structures
85
Reaction SitesTo specify a reaction site in a reaction query:
1. Click on the Reaction site tool .2. Click on a bond in the query that you want
to specify as a reaction site.
3. A table of options appears. Select the desired option. Click OK.
Structures
86
To specify a reaction site in a reaction query:
4. Repeat Steps 2 and 3 for other bonds in the
structure.
5. Save the modified query.
Structures
Reaction Sites
87
• Over-specification of bond sites and atom Over-specification of bond sites and atom mapping may cause the loss of relevant answersmapping may cause the loss of relevant answers.
• Specify only the minimum requirements needed to Specify only the minimum requirements needed to
eliminate non-relevant answers.eliminate non-relevant answers.
Structures
88
For the search query in this example, oneone H–N and oneone O=N bond is specified as XC.
Bonds with site specifications on them have an asterisk (*) over the bond.
Reaction Sites
Structures
89
Determine the impact of the change you made with another SAMPLE search.
=> Uploading rx2b.strL3 STRUCTURE UPLOADED=> D L3L3 HAS NO ANSWERSL3 STR
Structure attributes must be viewed using STN Express query preparation.
HN
CbCl
H
ON
CbCl
O
Structures
90
=> S L3 SSS SAM
SAMPLE SEARCH INITIATED 15:22:14 FILE 'CASREACT'
SCREENING COMPLETE - 453 REACTIONS TO VERIFY FROM 113 DOCUMENTS
100.0% DONE 453 VERIFIED 0 HIT RXNS 0 DOCS
SEARCH TIME: 00.00.04
FULL FILE PROJECTIONS: ONLINE **COMPLETE**
BATCH **COMPLETE**
PROJECTED VERIFICATIONS: 7785 TO 10335
PROJECTED ANSWERS: 0 TO 0
L4 0 SEA SSS SAM L3(0 REACTIONS)
A SAMPLE search searches the same portion of the database each time, so you can easily see the impact of the changes you made.
Structures
91
=> S L3 SSS FULL
FULL SEARCH INITIATED 15:41:00 FILE 'CASREACT'
SCREENING COMPLETE -11605 REACTIONS TO VERIFY FROM 2604 DOCUMENTS
100.0% DONE 11605 VERIFIED 14 HIT RXNS 7 DOCS
SEARCH TIME: 00.00.02
L5 7 SEA SSS FUL L3 (14 REACTIONS)
=> D SCAN
L5 7 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Functional group oxidation using sodium perborate
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1
o o o
RX(7) OF 69Cl
NH2
NO2
Cl92%
R:90568-23-3, AcOH
Structures
92
=> D L5 1-7L5 ANSWER 1 OF 7 CASREACT COPYRIGHT 2000 ACS
L5 ANSWER 2 OF 7 CASREACT COPYRIGHT 2000 ACS
L5 ANSWER 3 OF 7 CASREACT COPYRIGHT 2000 ACS
o o o
RX(2) OF 6
Cl
Cl
NH2
NO2
Cl
Cl
38%
C:41867-66-7, K H persulfate, Me2CO
REF: Eur. J. Inorg. Chem., (12), 2319-2325; 1999NOTE: PHOSPHATE BUFFER USED
RX(3) OF 3
OMe
CO2HCl
H2N(step 1)
OMe
CO2H
O2N
Cl
60%
1. NaBO3, AcOH2. Water
REF: Eur. J. Med. Chem., 30(10), 757-62; 1995
The default format displays the first hit reactions and its associated reference.
RX(22) OF 83
PhCl C
ONH2
PhNO2
Cl C
O59%
H2O2, (CF3CO)2O, CH2Cl2
REF: J. Med. Chem., 33(8), 2296-304; 1990
Structures
93
L5 ANSWER 5 OF 7 CASREACT COPYRIGHT 2000 ACS
L5 ANSWER 6 OF 7 CASREACT COPYRIGHT 2000 ACS
L5 ANSWER 7 OF 7 CASREACT COPYRIGHT 2000 ACS
RX(9) OF 14
O2NCl
NH2
(step 1)
NO2
O2NCl60%
1. NaNO2, HBF4, Water2. MeSO2Cl, THF
REF: J. Chem. Soc., Perkin Trans. 2, (6), 573-8; 1989
RX(7) OF 69Cl
NH2
NO2
Cl92%
R:90568-23-3, AcOH
REF: Tetrahedron, 43(8), 1753-8; 1987
RX(5) OF 16
CF3F3C
ClCl
S
O
O
S
NH2
O
O
NO2
CF3F3C
ClCl
S
O
O
S
O
O
86%
H2O2, H2SO4, Oleum
REF: Zh. Org. Khim., 23(3), 601-6; 1987
Structures
94
Many types of reaction structure queries
may be searched in CASREACT:
A + B => C (two reactants leading to a product)
A + B = > ? (two reactants going to any product)
A => ? (reactant going to any product)
? => B (any reactant going to a specific product)
Structures
95
Search Question:Locate methods for converting the two starting
materials shown below to the specified ether.
R = anything, including hydrogenBenzene rings may have other rings fused onto themAny substitution at all open sites
Structures
96
3. Save the query.
2. Specify reaction roles.
1. Build the structure for each participant.
4. Run the search.
Structures
97
To specify the reaction role for the structure fragment(s): 1. Click on the Reaction role tool .
A box explaining how to specify a reaction role is displayed. Click OK
Structures
98
To specify the reaction role for the structure fragment(s): 2. Click an atom in the structure for which you want to
specify a role.A menu of roles displays. Select the desired role. Click OK
Structures
99
To specify the reaction role for the structure fragment(s): 3. Repeat Step 2 for each fragment in the query.
Structures
100
Use as many of the reaction precision tools as needed to retrieve the desired types of reactions.
For this query, specify as XC the bonds from the benzene ring to X in one reactant from nitro-benzene ring to O in the product
Structures
(If you want you can also map the oxygen atom)
101
=> Uploading rx3.str
L1 STRUCTURE UPLOADED
=> D L1
L1 HAS NO ANSWERS
L1 STR
Structure attributes must be viewed using STN Express query preparation.
X
NO2
O
X
O
NO2
X
Reaction roles do not display with the structures on STN.
Structures
102
=> S L1 SSS SAM
SAMPLE SEARCH INITIATED 16:20:47 FILE 'CASREACT'
SCREENING COMPLETE - 71 REACTIONS TO VERIFY FROM 8 DOCUMENTS
100.0% DONE 71 VERIFIED 1 HIT RXNS 1 DOCS
SEARCH TIME: 00.00.04
FULL FILE PROJECTIONS: ONLINE **COMPLETE**
BATCH **COMPLETE**
PROJECTED VERIFICATIONS: 915 TO 1925
PROJECTED ANSWERS: 1 TO 79
L2 1 SEA SSS SAM L1 (1 REACTIONS)
Structures
103
=> D SCAN
L2 1 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Polymer-supported bases in combinatorial chemistry: synthesis of aryl ethers from phenols and alkyl halides and aryl halides
ALL ANSWERS HAVE BEEN SCANNED
RX(14) OF 15NO2
F
Cl
OH+
O2N Cl
O
73%
Pyrimidopyrimidine, MeCN
Structures
104
=> S L1 SSS FULL
FULL SEARCH INITIATED 15:45:42 FILE 'CASREACT'
SCREENING COMPLETE - 239 REACTIONS TO VERIFY FROM 68 DOCUMENTS
100.0% DONE 239 VERIFIED 9 HIT RXNS 6 DOCS
SEARCH TIME: 00.00.01
L3 6 SEA SSS FUL L1 (9 REACTIONS)
Structures
105
=> D SCANL3 6 ANSWERS CASREACT COPYRIGHT 2000 ACSTI 3-(3-Aryloxyphenyl)-1-(substituted methyl)-s-
triazine-2,4,6-trione or -thiotrione herbicidal agents
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1
(continued on next page)
RX(3) OF 6
MeO
NO2
FO
N
N
CH2
O
NH
C
O
O
+
Cl
Cl
OH
OMeNO2
Cl
Cl O
N NCH2
O NH
C
O
O
O
K2CO3, DMF
Structures
106
L3 6 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Synthesis of 2-alkoxy-5-nitrobenzamides by phase-transfer catalyzed nucleophilic substitution of 2-chloro-5-nitrobenzamides
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):0
RX(19) OF 19
NHBu-n
NO2
ClC
O
+
Cl
Cl
Cl
OH
NHBu-n
NO2Cl
Cl
Cl
O
C
O
Bu4N.Br, NaH, PhMe
NOTE: FAILED REACTION
Note how "failed reactions" display.
Structures
107
Precision tools are available in STN Express to focus on the desired types of reactions
To assign a Use the
Reaction direction Reaction Arrow Tool
Fragment roleReaction Role Tool
Bond that ischanged/unchangedin the reaction
Reaction Site Tool
Mapping between anatom in the reactantand product
Reaction Mapping Tool
Structures
108
1. Locate methods for carrying out the following ring-forming reaction:
Additional substitution is allowed at all open sites
Additional ring fusion is allowed
The bond can be single, double, or triple
Skills Practice
109
fragments assigned product role:containing 10fragments assigned reactant/reagent role:containing 1reaction site bonds:19-20:CC node mappings:7:11 8:10 9:18
110
=> Uploading C:\Program Files\stnexp\Queries\w9a.str L1 STRUCTURE UPLOADED => l1SAMPLE SEARCH INITIATED 05:24:29SCREENING COMPLETE - 99 REACTIONS TO VERIFY FROM 18 DOCUMENTS 100.0% DONE 99 VERIFIED 12 HIT RXNS 2 DOCSSEARCH TIME: 00.00.01 FULL FILE PROJECTIONS: ONLINE **COMPLETE** BATCH **COMPLETE**PROJECTED VERIFICATIONS: 1384 TO 2576PROJECTED ANSWERS: 2 TO 124 L2 2 SEA SSS SAM L1 ( 12 REACTIONS)
111
=> l1 fullFULL SEARCH INITIATED 05:24:39SCREENING COMPLETE - 1807 REACTIONS TO VERIFY FROM 273 DOCUMENTS 100.0% DONE 1807 VERIFIED 134 HIT RXNS 30 DOCSSEARCH TIME: 00.00.01 L3 30 SEA SSS FUL L1 ( 134 REACTIONS)
112
=> d fhit 2
Ph N
S
O
H
**
**
A
Ph
Br
O
H**
B(1)
Ph
Ph
O
S
N
***
*
YIELD 64%C
113
New compounds registered only from CASREACT
114
New compounds• Reaction participants not found in Registry were
given CASRN, Index Name, Structure
Only occurrence of this compound is in CASREACT
Patent interest: CASREACT has the relevant art
115
New compounds
=> casreact/lc(notp)(ca or caplus or caold)/lc L1 63411 CASREACT/LC(NOTP)(CA OR CAPLUS OR CAOLD)/LC => d 1-30 lc L1 ANSWER 1 OF 63411 REGISTRY COPYRIGHT 2005 ACS on STN LC STN Files: CASREACT. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . => 408508-10-1L2 1 408508-10-1 => l1 and l2L3 1 L1 AND L2
116
In CASREACT there are two main ways for searching:
Structures
Functional Groups
117
Functional Groups
Create reaction queries using the functional group tool in STN Express
Search for broadly defined transformations using functional groups
Specify non-reacting functional groups
118
While structure queries could be created to search for broadly defined reactions, this approach may:
Not run to completion within system limits Take a long time to complete
Functional Groups
119
Consider using functional group queries when you:
Want an overview of current methods being used to carry out a broadly-defined transformation
Are not retrieving answers with a precisely defined structure query Are looking for a broadly defined transformation in the presence of a
non-reacting functional group Want a set on which you run a subset search
Functional Groups
120
Functional group terms are assigned to approximately 200 different structural groups in CASREACT. Groups are identified as:
Reacting functionalities Formed functionalities Non-reacting functionalities
Functional Groups
121
Functional groups are divided into terms for
Rings Functionalities
Functional Groups
122
Ring Terms
1,2-C3N2 1,3-C3O2 1,4-C5N2
1,2-C3NO 1,3-C3OS C2S
1,2-C3NS 1,3-C3S2 C3N
1,2-C3O2 1,3-C4N2 C3O
1,2-C3OS 1,3-C4NO C3S
1,2-C3S2 1,3-C4NS C4N
1,2-C4N2 1,3-C4O2 C4O
1,2-C4NO 1,3-C4OS C4S
1,2-C4NS 1,3-C4S2 C5N
1,2-C4O2 1,4-C4N2 C5O
1,2-C4OS 1,4-C4NO C5S
1,2-C4S2 1,4-C4NS C6N
1,3-C3N2 1,4-C4O2 C6O
1,3-C3NO 1,4-C4OS C6S
1,3-C3NS 1,4-C4S2
Functional Groups
123
Ring terms describe 5- and 6-membered rings with any type of bonding.
For example:The term 1,3–C3NS describes this type of ring
where the N and S are in the 1 and 3 positions and other rings may be fused to the structure.
Functional Groups
124
Functionality Terms
ACETAL HALOHYDRIN PHOSPHITE ACETYL HEMIACETAL PHOSPHONATE ACID HALIDE HETEROCYCLES PHOSPHONIUM ACYCLIC ALKENE HYDRAZIDE PHOSPHORUS YLIDE ACYCLIC KETONE HYDRAZINE PI-ALKENE ACYLMETAL HYDRAZONE PI-ALKYNE ALCOHOLS HYDROPEROXIDE PI-ALLYL ALDEHYDE HYDROXYLAMINE PRIMARY ALCOHOL ALKENES IMIDE PRIMARY AMINE ALKYL HALIDE IMINE PURINE ALKYNE IMINO ETHER QUATERNARY AMMONIUM ALKYNES ISOCYANATE S-O GROUP ALLENE ISONITRILE SE GROUP ALLYL ALCOHOL ISOTHIOCYANATE SECONDARY ALCOHOL ALLYL HALIDE KETAL SECONDARY AMINE AMIDE KETENE SELENIDE AMIDINE KETENIMINE SELENOL AMINE OXIDE KETONES SILYL AMINES LACTAM SILYL ENOL ETHER ANHYDRIDE LACTONE SULFENYL HALIDE ARYL HALIDE MESYL SULFIDE ARYLSULFONYL METAL ARENE SULFINATE AZIDE ENOL METAL CARBENE SULFINYL HALIDE AZINE METAL CARBONYL SULFONAMIDE AZIRIDINE METAL CYCLOPENTADIENYL SULFONE AZO METAL HALIDE SULFONYL HALIDE AZOXY METAL HYDRIDE SULFONYLOXY CARBAMATE METAL METAL BOND SULFOXIDE CARBONATE METAL NITROGEN SULFUR YLIDE CARBONATE DERIVATIVES METAL NITROSYL TE GROUP o o o
Functional Groups
125
Functionality Terms
o o o CARBOXY DERIVATIVES METAL PHOSPHINE TERTIARY ALCOHOL CARBOXYLATE METAL SULFUR TERTIARY AMINE CARBOXYLIC METALLOCARBOCYCLE THIOACETAL CEPHEM MU-CARBONYL THIOAMIDE CHLORAMINE NITRILE THIOCARBONYL CYANAMIDE NITRILE OXIDE THIOCARBOXY CYANATE NITRITE THIOCYANATE CYANOHYDRIN NITRO THIOKETAL CYCLIC ALCOHOL NITRONE THIOL CYCLIC ALKENE NITROSAMINE THIONE CYCLIC KETONE NITROSO THIOPHENOL CYCLOPROPYL NITROXIDE THIOUREA DIAZO NULL TRIAZENE DIAZONIUM O-QUINONE TRIHALIDE DIENE ORGANOMETAL UNSATD ACID DIIMIDE ORGANOMETALLICS UNSATD ALDEHYDE DISULFIDE ORTHO ESTER UNSATD AMIDE ENAMINE OXIME UNSATD ESTER ENOL OXONIUM UNSATD KETONE ENOL ETHER P-N GROUP UNSATD NITRILE ENYNE P-O GROUP UNSATURATED ACID EPISULFIDE P-QUINONE UNSATURATED ALDEHYDE EPOXIDE P-S GROUP UNSATURATED AMIDE ETHER PENAM UNSATURATED ESTER GEM-DIHALIDE PEROXIDE UNSATURATED KETONE GLYCOL PEROXY ACID UNSATURATED NITRILE GUANIDINE PEROXY UREA HALIDES PHENOL VIC-DIHALIDE HALOFORMATE PHOSPHATE VINYL HALIDE
Functional Groups
126
Search Question:
Locate methods for converting a nitroso group to a primary amine.
Functional Groups
127
3. Upload the reaction query.
2. Logon to STN and enter CASREACT.
1. Build and save the functional group reaction
query.
Functional Groups
128
5. Display the results.
4. Run the reaction search.
Functional Groups
129
• Functional group queries are created in the structure drawing window of STN Express.
• Building a functional group query is accomplished in four steps:
a) Select the functional groups for the query
b) Assign reaction roles to functional groups
c) Do mapping
d) Save the query
Functional Groups
130
Click on the Functional Group button .
In "functional group mode" the current atom box changes to functional group terms, and all structure drawing tools are inactive.
Functional Groups
131
Click on the current atom box. An alphabetical listing of all functional group terms and their definitions appears:
RC = the atom can be in a ring or chainCON E2 = only 2 connections on the atomCSE = Chain Single Exact bondCDE = Chain Double Exact bond
Functional Groups
132
Click on the name of the desired functional group and select Single Use or Multiple Use. Click at the position on the structure drawing screen where you want to position the functional group.
Functional Groups
133
Repeat Step 3 for each functional group in the query.
Functional Groups
134
1. Click on the Reaction role tool .
2. Click on the functional group to which you want to assign a role. A box with all of the functional group roles appears.
Functional Groups
135
Select the role that applies to the functional group. Click OK.
3. Click on the next functional group and repeat Step 2 for it.
Functional Groups
136
Functional Groups
137
Use the Atom MappingAtom Mapping Tool to guarantee that at least one atom from the reacting group appears in the formed group. Atom map numbers appear on the screen
1 1
Functional Groups
138
Save the functional group query using the same procedure used to save a structure query.
Functional Groups
139
Functional Groups
140
• Proximity can be changed depending on the desired precision:– (L) proximity does not require mapping between
reacting functional groups and forming functional groups
– (S) proximity requires that at least one atom in the reacting functional group also be in the forming functional group
141
Upload the query
=> FILE CASREACT
=> QUE (NITROSO/FG.RXN (S) PRIMARY AMINE/FG.FORM)
L1 QUE (NITROSO/FG.RXN (S) PRIMARY AMINE/FG.FORM) The functional group query is converted to a 'text'
query when you save it.
The 'text' query includes search fields:
Reacting functional groups (/FG.RXN) Formed functional groups (/FG.FORM) The (S) operator which maps one atom from the
reacting group to an atom in the product group
The uploaded "text" query is assigned an L-number.
Functional Groups
142
For a functional group query, as with any other text
query, you cannot specify a search type (SSS/CSS)
or a search scope (SAM/FULL).
Run the search
=> S L1
562 NITROSO/FG.RXN
13296 PRIMARY AMINE/FG.FORM
L2 78 (NITROSO/FG.RXN (S) PRIMARY AMINE/FG.FORM) Each answer to a functional group
search is a document record containing one or more reactions that match the specified transformation.
Functional Groups
143
Display the results
=> D SCAN
L2 78 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Reactions of trimethyl- and triethylaluminum with 2,4,6-tri-tert-butylnitrosobenzene
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):2
RX(1) OF 2
Bu-t
t-Bu
t-Bu
NO
(step 1)
Bu-t
t-Bu
t-Bu
NH2+
20%
Bu-t
t-Bu
t-Bu
N
CH2O
+
25%
Bu-t
t-Bu
t-Bu Me
N OH+
28%
Bu-t
t-Bu
t-Bu Me
NHO
18%
1. AlMe3, THF2. Water
Functional Groups
144
L2 78 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI [7-15N]guanosine-labeled oligonucleotides as a nuclear magnetic resonance probe for protein- nucleic acid interaction in the major groove
L2 78 ANSWERS CASREACT COPYRIGHT 2000 ACS
TI Process for the reductive halogenation of aromatic nitro or nitroso compounds to haloaromatic amines
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):0
RX(2) OF 15
15N ONH2
NH
ONH2N
15NH2NH2
NH
ONH2N
Na2(S2O4), Water
RX(1) OF 4N O
F
NH234%
NH2+
34%
Pb, HF
Functional Groups
145
Search Question:
Find out more about this D SCAN hit:
TI A new and efficient method for the selective reduction of nitroarenes: use of ammonium sulfate- sodium borohydride
RX(11) OF 13N O NH2
90%
1. NaBH4, (NH4)2SO4, EtOH2. Water, Et2O
Functional Groups
146
3. Display the resulting answer in more detail.
2. Search the answer L-number AND word/TI.
1. Select a unique word from the title.
To display a D SCAN answer in more detail
Functional Groups
147
=> S L1 AND NITROARENES/TI 562 NITROSO/FG.RXN 13296 PRIMARY AMINE/FG.FORM 78 (NITROSO/FG.RXN (S) PRIMARY AMINE/FG.FORM) 69 NITROARENES/TIL3 1 L1 AND NITROARENES/TI
=> D L3 1 BIB ABSL3 ANSWER 1 OF 1 CASREACT COPYRIGHT 2000 ACSAN 123:338641 CASREACTTI A new and efficient method for the selective reduction of nitroarenes: use of ammonium sulfate- sodium borohydrideAU Gohain, Sujata; Prajapati, Dipak; Sandhu, Jagir S.CS Reg. Res. Lab., Assam, 785 006, IndiaSO Chem. Lett. (1995), (8), 725-6
o o o
Functional Groups
148
o o oCODEN: CMLTAG; ISSN: 0366-7022DT JournalLA EnglishGI
AB Nitroarenes I (R = NO2; R1 = e.g., 4-Cl, 2-, 4- CO2H, 4-Ac, 4-cyano, 3-vinyl) were selectively and rapidly reduced to 75-90% corresponding amino compds. I (R = NH2) using (NH4)2SO4-NaBH4. This method is typically complete in 30 min and shows no byproducts usually seen using other methods.
R
R1
I
Functional Groups
149
Search Question:
Locate methods for converting a primary alcohol to an aldehyde in the presence of a non-reacting secondary alcohol.
Functional Groups
150
The secondary alcohol is assigned a non-reacting role.
1 1
Only the reacting group is mapped to the product.
Functional Groups
151
Functional GroupsSave it then click on:
152
=> FILE CASREACT
=> QUE SECONDARY ALCOHOL/FG.NON (L) (PRIMARY ALCOHOL/FG.RXN (S) ALDEHYDE/FG.FORM)
L1 QUE SECONDARY ALCOHOL/FG.NON (L) (PRIMARY ALCOHOL/FG.RXN (S) ALDEHYDE/FG.FORM)
=> S L1 19805 SECONDARY ALCOHOL/FG.NON 35627 PRIMARY ALCOHOL/FG.RXN 14977 ALDEHYDE/FG.FORML2 217 SECONDARY ALCOHOL/FG.NON (L) (PRIMARY ALCOHOL/FG.RXN (S) ALDEHYDE/FG.FORM)
Functional Groups
153
=> D SCANL2 217 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Selective oxidation of primary hydroxy groups in primary-secondary diols
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1
RX(1) OF 1
(CH2)5 MeMe
OH
HO
(CH2)5 MeMe
CHO
OH
82%
Bu4NCl, NaOCl, Me4-piperidoxyl, NaHCO3, KBr, CH2Cl2, Water
Functional Groups
154
L2 217 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Total synthesis of (+)-compactin by a double Michael protocol
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1
RX(78) OF 409 - 3 STEPS
Me
HOOH
H
H
Si(Pr-i)3
Me
OHC OH
H86%
1. Pivaloyl chloride, Pyridine2.1. (i-Pr)3Si O3SCF3, Et3N, CH2Cl22.2. LiAlH4, Et2O3.1. (COCl)2, DMSO, CH2Cl23.2. Et3N
NOTE: 2) (99%/99%)
Functional Groups
155
L2 217 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Prostanoid and related compounds. Part II. Synthesis of biologically active 6-azaprostacyclin derivatives
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):0
RX(6) OF 69
OMeHO
HON
O O
H
H
OMe
OHC
HON
O O
H
H
NOTE: Pfitzner-Moffatt reagent
Functional Groups
156
When a reaction is entered into the CASREACT database, the most precise functional group term that applies to a structure group is assigned. Broader functional group terms are not also assigned.
Example: For this structure:
The functional group term ENOL is assigned, but the terms SECONDARY ALCOHOL and ACYCLIC ALKENE are not.
Functional Group Classes
H
Functional Groups
157
Use class terms, which encompass specific functional group terms for that class, to search for all specific functionalities in a broader functional group.
Class Terms
Alcohols Carboxy derivatives
Alkenes Halides
Alkynes Heterocycles
Amines Ketones
Carbonate derivatives Organometallics
Functional Groups
Functional Group Classes
158
ALCOHOLS ALLYL ALCOHOLCYANOHYDRIN CYCLIC ALCOHOLENOL GLYCOL HALOHYDRIN
HEMIACETAL HYDROXYLAMINEPHENOL PRIMARY ALCOHOLSECONDARY ALCOHOL TERTIARY ALCOHOL
ALKENES ACYCLIC ALKENECYCLIC ALKENE
ALKYNES ALKYNE ENYNE PI-ALKYNE
AMINES AMINE OXIDE AZIRIDINE CHLORAMINE CYANAMIDE ENAMINE
HYDROXYLAMINEIMINE PRIMARY AMINE SECONDARY AMINETERTIARY AMINE
Functional Group Classes
Functional Groups
159
CARBONATEDERIVATIVES
CARBAMATE CARBONATE GUANIDINE
HALOFORMATE THIOUREA UREA
CARBOXYDERIVATIVES
ACID HALIDE AMIDE AMIDINE ANHYDRIDECARBOXYLATE CARBOXYLIC HALOFORMATE
IMIDE LACTAM LACTONE PEROXY ACIDPEROXY ESTER THIOAMIDE THIOCARBOXY
HALIDES ACID HALIDE ALKYL HALIDE ALLYL HALIDEARYL HALIDE CHLORAMINE GEM-DIHALIDE HALOFORMATE
METAL HALIDE SULFENYL HALIDE SULFINYL HALIDE SULFONYL HALIDE TRIHALIDEVIC-DIHALIDE VINYL HALIDE
Functional Groups
Functional Group Classes
160
HETEROCYCLES 1,2-C3N2 1,2-C3NO 1,2-C3NS 1,2-C3O21,2-C3OS 1,2-C3S2 1,2-C4N2 1,2-C4NO 1,2-C4NS 1,2-C4O2 1,2-C4OS1,2-C4S2 1,3-C3N2 1,3-C3NO 1,3-C3NS 1,3-C3O2 1,3-C3OS 1,3-C3S21,3-C4N2 1,3-C4NO 1,3-C4NS 1,3-C4O2 1,3-C4OS 1,3-C4S2 1,4-C4N2
1,4-C4NO 1,4-C4NS 1,4-C4O2 1,4-C4OS 1,4-C4S2 1,4-C5N2 C2S C3N C3O C3S C4N C4O C4S C5N C5O C5S C6N C6O C6SAZIRIDINE CEPHEM EPISULFIDE EPOXIDE PENAM PURINE
Functional Groups
Functional Group Classes
161
KETONES ACYCLIC KETONE CYCLIC KETONE O-QUINONEP-QUINONE
ORGANOMETALLICSACYLMETAL METAL ARENE METAL CARBENE METAL CARBONYLMETALCYCLOPENTADIENYLMETAL HALIDE METAL HYDRIDE METAL METAL BOND METAL NITROGEN
METAL NITROSYL METAL PHOSPHINE METAL SULFUR METALLOCARBOCYCLEMU-CARBONYLORGANOMETAL PI-ALKENE PI-ALKYNE PI-ALLYL
Functional Groups
Functional Group Classes
162
Search Question:
Locate methods for converting secondary alcohols or cyclic alcohols to ketones.
Functional Groups
163
To search all relevant functional group terms in one step, combine the terms using the OR feature.
After
Selecting the functional groups Assigning the roles Mapping reactants to the product
Functional Groups
164
Click on the OR operator button and draw a box around the terms to be ORed.
1
1
1
Functional Groups
Cyclic alchools
Secondary alchools
1
Ketones1
1
165
=> FILE CASREACT=> QUE KETONES/FG.FORM (S) (SECONDARY ALCOHOL/FG.RXN OR CYCLIC ALCOHOL/FG.RXN)L1 QUE KETONES/FG.PRO (S) (SECONDARY ALCOHOL/FG.RXN OR CYCLIC ALCOHOL/FG.RXN)
=> S L1 52307 KETONES/FG.PRO 30715 SECONDARY ALCOHOL/FG.RXN 2207 CYCLIC ALCOHOL/FG.RXNL2 6586 KETONES/FG.PRO (S) (SECONDARY ALCOHOL/FG.RXN OR CYCLIC ALCOHOL/FG.RXN)=> D SCANL2 6586 ANSWERS CASREACT COPYRIGHT 2000 ACSTI Exceptionally potent inhibitors of fatty acid amide hydrolase: the enzyme responsible for degradation of endogenous oleamide and anandamide
Functional Groups
166
RX(4) OF 57
(CH2)7 (CH2)7Me
OH
N
O
(CH2)7 (CH2)7Me
O
N
O
67%
Martin's reagent, CH2Cl2
NOTE: STEREOSELECTIVE
Functional Groups
167
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):1L2 6586 ANSWERS CASREACT COPYRIGHT 2000 ACSTI An enantiodivergent route to .alpha.-cuparenone utilizing chiral cyclopentenol having a latent meso structure
HOW MANY MORE ANSWERS DO YOU WISH TO SCAN? (1):0
RX(5) OF 113
Me
Me Me
Me
Ph
OO
O
OH
H
H
Me
Me Me
Me
Ph
OO
O
O
H
H
96%
Martin's reagent
Functional Groups
168
Summary Functional group terms can be used to search for broadly defined transformations
Functional groups terms are available for
Reactants
Reagents Products
Functional groups are identified as Reacting functionalities
Formed functionalities Non-reacting functionalities
Functional Groups
169
Functional group queries are easily created in the structure drawing window of STN Express
"Class terms" can be used to search for broad classes of functional groups
Search relevant functional group terms in one step by combining them with the OR operator
Functional Groups
Summary
170
1. Locate reactions in which sulfides are converted to sulfones.
2. Locate reactions in which acyl halides are converted to alcohols in the presence of non-reacting primary amines.
3. Locate reactions in which hydrazines are used to prepare the following type of diazoles:
Skills Practice
171
=> fil casreact => que SULFIDE/fg.rxn (L) SULFONE/fg.form L1 QUE SULFIDE/FG.RXN (L) SULFONE/FG.FORM => l1 26225 SULFIDE/FG.RXN 6113 SULFONE/FG.FORML2 3557 SULFIDE/FG.RXN (L) SULFONE/FG.FORM
1
172
=> d fhit L2 ANSWER 1 OF 3557 CASREACT COPYRIGHT 2004 ACS on STN RX(7) OF 692 ...AC ===> AF...
RX(7) RCT AC 5651-88-7 RGT AG 37222-66-5 Oxone PRO AF 2525-40-8 SOL 67-56-1 MeOH, 7732-18-5 Water
PhS CH2 C CH
AC(7)
PhSOO
C CH
**
YIELD 93%AF
1
173
=> d fcrdref L2 ANSWER 1 OF 3557 CASREACT COPYRIGHT 2004 ACS on STN
RX(7) OF 692
PhS CH2 C CH Ph S CH2
O
OC CH
93%
Oxone, MeOH, Water
REF: Heterocycles, 62,, 583-618; 2004
1
174
=> fil casreact => que PRIMARY AMINE/fg.non(L)(ACID HALIDE/fg.rxn(S)ALCOHOLS/fg.form) L1 QUE PRIMARY AMINE/FG.NON(L)(ACID HALIDE/FG.RXN(S)ALCOHOLS/FG.FORM) => l1 14761 PRIMARY AMINE/FG.NON 36978 ACID HALIDE/FG.RXN 123464 ALCOHOLS/FG.FORML2 3 PRIMARY AMINE/FG.NON(L)(ACID HALIDE/FG.RXN(S)ALCOHOLS/FG.FORM)
2
175
=> d fhit 2 L2 ANSWER 2 OF 3 CASREACT COPYRIGHT 2004 ACS on STN RX(1) OF 1 A ===> B RX(1) RCT A 39878-87-0 RGT C 16940-66-2 NaBH4 PRO B 56613-80-0 SOL 110-71-4 (CH2OMe)2
Ph
ClNH2
O
**
HCl
A(1)
Ph
NH2O
H
H **
*
YIELD 87%B
2
176
3
=> fil casreact => que 1,2-C3N2/fg.form L1 QUE 1,2-C3N2/FG.FORM => l1L2 6679 1,2-C3N2/FG.FORM
177
3
=> Uploading C:\Program Files\stnexp\Queries\fg6.str
chain nodes :1 2 chain bonds :1-2 exact/norm bonds :1-2 Match level :1:CLASS 2:CLASS fragments assigned reactant/reagent role:fragments assigned reactant/reagent role:containing 1containing 1L3 STRUCTURE UPLOADED
178
3
=> l3 full subset=l2FULL SUBSET SEARCH INITIATED 11:06:28SCREENING COMPLETE -55237 REACTIONS TO VERIFY FROM 5883 DOCUMENTS 100.0% DONE 55237 VERIFIED 47288 HIT RXNS 4821 DOCSSEARCH TIME: 00.00.01 L4 4821 SEA SUB=L2 SSS FUL L3 ( 47288 REACTIONS)
179
3
=> d fhit L4 ANSWER 1 OF 4821 CASREACT COPYRIGHT 2004 ACS on STN RX(12) OF 23 Y + Z ===> A...
MeMe
OO
H
**
**
Y
NNH
N
H
H
* *
*
Z(12)
Me
Me NN
N
****
A
180
3
=> d fhit 2 L4 ANSWER 2 OF 4821 CASREACT COPYRIGHT 2004 ACS on STN RX(4) OF 8 O + P ===> Q
EtO
OEt
Ph
P NO
NH
H
H*
*
O
Ph
Ph
NC
S
SCN * ***
P(4)
EtO OEt
PhPh
NC
P
N
O
N
NH
S
H**
**
**
YIELD 50%Q
181
Refining Results
In this section, you will learn to:
• Restrict results to reactions with yields above a given value• Restrict results to single-step reactions • Specify that a specific catalyst, reagent, or solvent is present or not
in the reaction• Include reaction note information in the refinement
182
Several reaction search fields are available for refining reaction search results.
When you want to Use this search field
Restrict results by yield /YD
Restrict results by number of steps /NS
Require/eliminate a specific reactionparticipant using its
CAS RN and
Reaction role
Solvent
Catalyst
Reagent
Reactant
Reagent or Reactant
Product
Not a product
/SOL
/CAT
/RGT
/RCT
/RRT
/PRO
/NPRO
Specify terms from the reaction NOTE Basic Index
Refining Results
183
Use these fields to refine the reactions in answer sets from:
Structure searches Functional group searches
Since each answer in CASREACT may contain more than one reaction, you must use the (L) operator to apply the refinement to the "hit" reactions in the answer set.
Refining Results
184
Yields are reported for many, but not all, reactions in CASREACT. Yields are whole number percent values, e.g., 75%. They may be searched as numeric ranges, e.g., YD>80 for yield greater than 80%. To isolate reactions without yields, use the term NON/YDT.
Refining Results
185
Helpful Hint
Use (L) to require that one of the products in the hit reaction have the specified yield. In reactions with more than one product, the specified yield may apply to a product other than the "hit" product.
If you retrieved the reactions using a Structure search query CAS RN for the product
Then use the (A) operator to specify that the yield applies to the hit product.
Refining Results
186
The number of steps in a reaction is searched as a numeric range, e.g., 1/NS for single-step reactions.
Helpful Hint
'Pot' reactions are considered to be single-step reactions.
Refining Results
187
Reaction participants can be specified by a:
CAS RN (Solvents and catalysts can only be specified with CAS RNs) Registry L-number
Refining Results
188
To specify the role the CAS RN plays in the reaction, use one of these fields:
Use this field To specify this role
/SOL Solvent
/CAT Catalyst
/RGT Reagent
/RCT Reactant
/RRT Reagent or Reactant
/NPRO Not a Product
/PRO Product
189
Examples
Use this strategy If you want to
=> S L1 (L) 7440-05-3/CAT Limit the hit reactions in L1 to thosecatalyzed by palladium (7440-05-3)
=> S L1 (L) ANY/CAT Limit the hit reactions in L1 tocatalytic reactions
=> S L1 (L) 64-19-7/NPRO Limit the hit reactions in L1 to those inwhich acetic acid (64-19-7) is sometype of starting material
=> S L1 (NOTL) 108-24-7/RRT Eliminate the hit reactions from L1where acetic anhydride (108-24-7) isused as a reactant or reagent
Refining Results
190
The NOTE field contains additional information about the reaction that cannot be specified in the reaction diagram via a structure or CAS RN, e.g.,
Safety information
RX(17) OF 46 - 2 STEPS
OMeNO2
NO2O2N
ClNH2
NH2
NH2
H2N
H2N
1. NH3, MeOH2. Pd, H2, MeOH
NOTE: 1) explosive compd.
Refining Results
191
Reaction conditions
RX(6) OF 12
Pr-nPh
PhCH2 O CO
O
OPh
PhOH
O
O80%
Lipase
NOTE: enzymic
RX(17) OF 19 - 2 STEPS
AcO
AcO
OAc
OMe
O
O
AcOOAc
AcOOMe
BrO
C
O
47%
1. Pd, H2, MeOH2. Bromosuccinimide, Perbenzoic acid, CCl4
NOTE: 2) photochem.
Refining Results
192
Failed reactions
Participants not indexed via CAS RNs
RX(3) OF 5
Br BrCH2 CH2SiH2 SiH2
OMe
NSiH2SiH2
MeONH2, Et3N
NOTE: Failed reaction
RX(3) OF 47
(CF2)3 CF3S
O
HO(CF2)3 CMe2F3C S CH2
O
O
CH
60%
Isopentadiene
NOTE: Petroleum ether
Refining Results
193
Helpful HINT
Individual words from the NOTE are in the Basic
Index and may be searched. Use truncation and synonyms for best results when
searching NOTE words.
Example:
=> S L1 (L) PHOTOCHEM?
Refining Results
194
Refining Results
NS N
OO
Find reactions: With yield > 50% Using solvent CHCl3
Catalyzed
195
Refining Results=> fil casreactL1 STRUCTURE UPLOADED => dL1 HAS NO ANSWERSL1 STR
NS N
OO
196
Refining Results
=> l1 fullFULL SEARCH INITIATED 11:19:15SCREENING COMPLETE - 33 REACTIONS TO VERIFY FROM 20 DOCUMENTS 100.0% DONE 33 VERIFIED 10 HIT RXNS 8 DOCSSEARCH TIME: 00.00.01 L2 8 SEA SSS FUL L1 ( 10 REACTIONS)
197
Refining Results
=> l2(a)yd>50 272798 YD>50L3 3 L2(A)YD>50 => d fhit L3 ANSWER 1 OF 3 CASREACT COPYRIGHT 2003 ACS RX(4) OF 9 J ===> K
MeO
NH
S
H**
*
J(4)
MeO
C N*
YIELD 96%K
198
Refining Results=> l2(l)yd>50 272798 YD>50L4 3 L2(L)YD>50 => l2(l)67-66-3/sol 17914 67-66-3/SOLL5 1 L2(L)67-66-3/SOL
RX(4) RCT J 2362-64-3 RGT C 10026-07-0 TeCl4, D 121-44-8 Et3N PRO K 874-90-8 SOL 67-66-3 CHCl3
199
Refining Results=> l2(l)any/cat 123302 ANY/CATL6 2 L2(L)ANY/CAT => d fhit
RX(1) RCT A 2362-64-3 RGT C 7664-41-7 NH3 PRO B 874-90-8 CAT 7632-00-0 NaNO2
200
Me
CH2
CH
N
OH Me
CH2 N0-9 0-9
Locate syntetic methods for converting the following aliphatic aldoximes to nitriles
Skills Practice
201
=> fil casreact => que OXIME/fg.rxn (S) NITRILE/fg.form L1 QUE OXIME/FG.RXN (S) NITRILE/FG.FORM => Uploading C:\Program Files\stnexp\Queries\react.str. . . . . . . . . . . . . . fragments assigned product role:containing 6fragments assigned reactant/reagent role:containing 1reaction site bonds:4-5:CC node mappings:4:9
L2 STRUCTURE UPLOADED
202
=> l1 8112 OXIME/FG.RXN 11370 NITRILE/FG.FORML3 855 OXIME/FG.RXN (S) NITRILE/FG.FORM => l2 full subset=l3FULL SUBSET SEARCH INITIATED 03:24:57SCREENING COMPLETE - 2142 REACTIONS TO VERIFY FROM 668 DOCUMENTS 100.0% DONE 2142 VERIFIED 83 HIT RXNS 49 DOCSSEARCH TIME: 00.00.01 L4 49 SEA SUB=L3 SSS FUL L2 ( 83 REACTIONS)
203
=> d fhit L4 ANSWER 1 OF 49 CASREACT COPYRIGHT 2004 ACS on STN RX(39) OF 50 BM ===> B
RX(39) RCT BM 110-69-0 RGT C 5470-11-1 H2NOH-HCl, D 124-63-0 MeSO2Cl PRO B 109-74-0 CAT 1344-28-1 Al2O3 NTE green chem.-no solvent
Pr-nNHO
H
**
*
BM(39)
CH3C N*
YIELD 95%B
204
Find reactions concerning carbonilations of aromatic systems
Skills Practice
205
=> fil reg => carbon monoxide/cnL3 1 CARBON MONOXIDE/CN => fil casreact=> l3/nproL10 6536 L3/NPRO
206
=> Uploading C:\Program Files\stnexp\Queries\saguatti2.str chain nodes :4 5 6 ring nodes :1 2 3 . . . . . .normalized bonds :1-2 2-3 fragments assigned product role:containing 1reaction site bonds:2-4:CCL13 STRUCTURE UPLOADED
207
=> l13 full subset=l10FULL SUBSET SEARCH INITIATED 03:56:36SCREENING COMPLETE - 48032 REACTIONS TO VERIFY FROM 5937 DOCUMENTS 100.0% DONE 48032 VERIFIED 303 HIT RXNS 74 DOCSSEARCH TIME: 00.00.01 L15 74 SEA SUB=L10 SSS FUL L13 ( 303 REACTIONS)
208
=> d scan L15 74 ANSWERS CASREACT COPYRIGHT 2004 ACS on STN TI Manufacture of aromatic aldehydes
RX(1) OF 1
C O- +CH O
Benzene, C:129648-41-5
NOTE: photochem.
209
N N
O O
S
This reagent has been cited? Who sells it in Italy?
Skills Practice
210
=> fil reg=> c11h8n2o2s/mf and nc=1 and nrs=2 and 2 c5n/ea L1 3 C11H8N2O2S/MF AND NC=1 AND NRS=2 AND 2 C5N/EA => l1 and casreact/lc and chemcats/lc L2 2 L1 AND CASREACT/LC AND CHEMCATS/LC => d scan
211
L2 2 ANSWERS REGISTRY COPYRIGHT 2003 ACSIN Carbonothioic acid, O,O-di-2-pyridinyl ester (9CI)MF C11 H8 N2 O2 S
OCO
SNN
L2 2 ANSWERS REGISTRY COPYRIGHT 2003 ACSIN 2(1H)-Pyridinone, 1,1'-carbonothioylbis- (9CI)MF C11 H8 N2 O2 S
C
S
NN
OO
212
=> l2 and pyridinone 18237 PYRIDINONEL3 1 L2 AND PYRIDINONE => fil chemcats => l3 and italyL4 1 L3 AND ITALY => d hitCOMPANY INFORMATION SIGMA-ALDRICH S.r.l.Via Gallarate, 154Numero Verde: 167-827018Milano, 20151 Italy Phone: 39 2 3341 7310Fax: 39 2 3801 0737Email: [email protected] Registry No. (RN): 102368-13-8