the chemical information instructorfaculty.missouri.edu/~glaserr/4210f19/sources/info... · the...

the chemicalinformation instructor

edited byArleen Somerville

Carlson LibraryUniversity of Rochester

Rochester, NY 14627

Information Sources for Organic Chemistry, 1

Arleen N. SomervilleCarlson Library, University of Rochester, Rochester, NY 14627

Knowledge and understanding of the major informationsources enable students and professional chemists to findneeded information efficiently and on a timely basis. Learn-ing to select the optimum sources and use them efficientlyis an integral part of chemical literacy.

This article provides ready-fco-use lecture material aboutorganic chemistry information sources, a chart that linkssources with questions that is suitable for distribution tostudents, and a set of practice questions.

Organic chemists have information questions character-istic of their research. These questions generally fall intoeither of two, occasionally overlapping, groups: those re-lated to the synthesis or preparation of substances, or thoserelated to mechanistic or physical organic chemistry. Theformer group might include name reactions, reaction types,functional group transformations, solvents and reagents,synthesis or reactions of a class of compounds or specificcompounds, and preparative techniques. Questions in thesecond group might include problems involving the relationof structure to kinetics or equilibria, the structure of mole-cules or transition states, types of reaction mechanisms,and spectroscopic aspects of organic chemistry. Some ques-tions, such as those about stereochemistry, may arise undereither of the two groups, depending on the context or majorthrust of the query.

This, and succeeding columns, will offer a chart that liststhese categories of organic chemistry questions and sug-gests some optimum or typical sources. The reader shouldbe aware that such source lists are necessarily representa-tive rather than exhaustive, that certain sources may berelevant to more than one question category, and that some

degree of judgment or prioritization must be exercised inthe use of these lists. While the list of sources is not meantto be comprehensive, this chart helps develop efficientsearching skills and chemical information literacy. The fulllist is suitable for use with upper level undergraduates,graduate students, and professional chemists. For otherundergraduates, the instructor will want to include selec-tive sources relevant to their information questions.

In using this chart, chemists should identify the variousways that their questions can best be answered using thetabulated categories as guides. One could thus ask about a

synthesis question: Is a specific functional group transfor-mation involved? Would the use of a name reaction behelpful? Is a general type of reaction likely to be required?What reagent would be best? Has a similar substance beensynthesized? From such an analysis one can proceed to thechart to determine which sources to examine first. In cer-

tain cases more than one category should be consulted. Forexample, for a functional group interconversion, one canstart a search under functional transformations, but one

might supplement this search using sources listed under

reaction type or possibly under class of compounds. Specificfeatures of many sources are described and illustratedhere, so that the information can be used for lectures.Complete bibliographic information is provided in an al-phabetic list at the end of the article. This article coverssources for name reactions and reaction types; future arti-cles will describe sources for other categories.

Searching by Name ReactionClassic reactions of broad scope may be named after the

discoverers or developers of the reactions. These “name”reactions are important tools of organic chemists. Achemistmay ask:

What is the ester enolate version of the Claisen rearrangement?Has a recent article described use of the intramolecular Wittig

reaction ?

Can one find an example of the Corey-Kim oxidation?

Certain sources answer questions about such name reac-tions

Name Reaction: General Sources

1. Mundy. Name Reactions and Reagents in OrganicChemistry.An excellent, concise, easy to scan reference source.

The book is divided into two main sections: name reactions, andreagents used in name reactions.

For each name reaction, two pages provide the core informa-tion. Figures 1 and 2 show the two pages for the Claisenrearrangement.

Figure 1 provides a textbook reference for a general descriptionof the Claisen rearrangement, the general reaction scheme,the reaction mechanism, notes that augment the reactionscheme or mechanism or that amplify examples on the follow-ing page designated with a triangle, and selected major ref-erences keyed to examples on the following page.

Figure 2 lists five examples of the Claisen rearrangement,using reaction diagrams. The circled numbers link the exam-

ples to the references on the previous page.

2. March. Advanced Organic ChemistryA reference source for students and professional chemists.Part 1 covers information to help students understand mecha-

nisms including chemical bonding, stereochemistry, and theeffects of structure on reactivity. Part 2 is organized byreaction types, with chapters on aromatic nucleophilic andelectrophilic substitution, aliphatic nucleophilit^ and electro-philic substitution, free-radical substitution, eliminations,rearrangements, oxidations, reductions, additions to carbon-

Volume68 Number 7 July 1991 553

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Figure 1. First of two pages on the Claisen rearrangement fromMundy, Name Reactions and Reagents in Organic Chemistry. (Re-produced with permission of Wiley.)

carbon multiple bonds, and additions to carbon-hetero mul-tiple bonds.

Discusses scope, limitations, and mechanisms, and providesextensive references to journal articles for detailed experi-mental procedures.

Includes a detailed subject index that permits rapid location ofsuch name reactions as Cope rearrangement, Dieckmanncondensation, or Vilsmeier reaction.

3. Carey and Sundberg. Advanced Organic Chemistry.Part B.

A comprehensive textbook for advanced undergraduates andgraduate students, which professional chemists will use as a

reference manual.Describes synthetically useful reactions and their applications

in an easy-to-follow format using extensive reaction dia-grams, with references to journal articles and handbooks.

Provides an excellent description of such name reactions as

Wittig, Diels-Alder, Claisen rearrangement, Birch reduction,and Cope rearrangement, all of which can be found in theindex.

Many reaction mechanisms are given.Each chapter concludes with a selected list of general references

and practice questions.

4. Surrey. Name Reactions in Organic ChemistryOne of several books that offer brief definitions of name reac-

tions.Provides brief two page summaries of over 130 name reactions

of general interest. References refer to journal articles andbook chapters for more details.

Figure 2. Second page on the Claisen rearrangement from Mundy,Name Reactions and Reagents in Organic Chemistry. (Reproducedwith permission of Wiley.)

5. Organic ReactionsPublished approximately once per year since 1942.Contains extensive review chapters, each covering a single

reaction of wide application. Chapters cover:

•reaction mechanism•scope and limitations of the reaction•experimental conditions•experimental techniques•related synthetic processes•several detailed experimental procedures that illustratethe reaction. These procedures, unlike those in OrganicSyntheses, have not been checked in two laboratories,

•tables listing all examples of the reaction with comprehens-ive list of references to original journal articles

To locate relevant chapters, check the cumulative subject indexin the most recent volume. For example, the index for volumes1-39 is found at the back of volume 39. The 420-page

Vol. 112, 1990 - GENERAL SUBJECT INDEX

wittig Reaction

intramol.of oxoalkylphosphoranylideneacetates,

macrocyclic lactones by, 20831fof phosphoranylidenepropyl amides, 216607gof spiral isoquinoline phosphonate deriv.,

erythrinan derivs. from, 77666kintramol. cyclocondensation reaction and, of

acetylhydroxyxanthone with(carbethoxymethylene)t riphenylphospho rane,138936x

Figure 3. Intramolecular Wittig reaction found in CA General SubjectIndex, v. 112. (Reproduced with permission of American ChemicalSociety.)

554 Journal of Chemical Education

Beckmann Reactions chapter in volume 35 is found quicklyin the Index.

Caution: Be cautious about using reactions given in the oldvolumes. Although some reactions are classics, others are now

obsolete.

6. Chemical Abstracts (CA)A. A limited number of major, classic name reactions, such as

Wittig, Claisen rearrangement, Diels-Alder, and Grignardreactions, can be found in the General Subject Index or by a

computer search of CA.1. A search for articles on use of the intramolecular Wittig

reaction is illustrated in Figure 3. A check in the GeneralSubject Index of v. 112 (Jan.- June 19901 under “Wittigreaction, intramolecular” locates about four references.

To identify the first article, check the abstract number2083 If in v. 112. Figure 4 shows the article title, the authorand his affiliation, the abbreviated journal title, publica-tion year, volume and issue number, pages, language, andbrief summary of article.

112: 20831 f Cumulated ylides. II. Syntheses of (E)-a,(J-un-saturated macrocyclic lactones by intramolecular WitLig-olefinationvia tripheny Iphosphoranylideneketene. Bcstmann. Hans Juergen;Schobert. Rainer (foist. Org. Chem., Univ. Erlsngen-Nucmbcrg.D-8520 erlangen, Fed. Rep. Ger.). Synthesis 1989, (6), 419-23(Ger). Lactones I (n = 4, 6, 8; R = H, Me;RJ = H. Me, Pr. Et) were

O

obtained by reaction of acetals II with Ph3P+C-:CO and intramol.Wittig reaction. I (n = 4, 8, R = R* = H) were also obtained fromHO(CH2)n+4CHO and Ph3P+C-:CO. This reaction sequence was alsoused to prep. (±)-recifeiolide and ambrettolide. Exaltolide was

obtained by redn. of I (n = 8, R = R* = H).

Figure 4. CA abstract information for article found in Index. (Repro-duced with permission of American Chemical Society.)

2. Or, one can conduct a computer search of CA. (CA File on

STN International was used.) A search of 1990 CA forarticles about the intramolecular Wittig reaction is shownin Figure 5. A computer search not only matches Wittigreaction as a General Subject Index heading, but also whenit appears in the article title, keywords, and modifyingphrases of the Chemical Substance Index. Note the use of(L) to search for intramolecular specifically related toWittig reaction and the truncation symbol (?) to search forthe abbreviated and full forms of intramolecular. One ofthe 27 answers is shown in Figure 6.

B. Other name reactions are considerably more difficult to findin CA. A computer search of CA, with increased access towords and terms within the article title, keywords, subjectand substance indexing, and abstracts, may locate some rel-evant articles that use name reactions. Such a search is notcomprehensive, because the name of the name reaction maynot appear in the article title, indexing or abstract.

The computer search for articles about use of the Corey-Kimreaction should specify that the abstract and all parts of theBasic Index (BI) (article title, keywords, and indexing) shouldbe searched. Two of the five articles found are shown in Figure8.

Name Reaction: Specific Sources

Some name reactions are sufficiently important thatbooks are published about them. These sources provide

=> s wittig reaction (L) intramol? range=(1990,)

LI

963 WITTIG60709 REACTION

837 WITTIG REACTION(WITTIG(W)REACHON)

2742 INTRAMOL?27 WITTIG REACTION (L) INTRAMOL?

Figure 5. Computer search of CA for 1990 articles on intramolecularWittig reaction. (Reproduced with permission of American ChemicalSociety.)

Ll ANSWER 2 OF 27COPYRIGHT (C) 1991 AMERICAN CHEMICAL SOCIETY

CA114(7):61652h A novel synthesis of perfluoroalkylated.alpha.,.beta.-unsaturated carbonyl compounds. Sheri, Yanchang;Wang, Tielin (Shanghai Inst. Org. Chem., Acad. Sin., Shanghai200032, Peop. Rep. China). Tetrahedron Lett, 31(41), 5925-6 (Eng)1990. CODEN: TELEAY. ISSN: 00404039.

Figure 6. One article about the intramolecular Wittig reaction foundby computer search of CA. (Reproduced with permission of AmericanChemical Society.)

=> s (corey kim)/bi,ab

121 COREY/BI41 KIM/BI4 (COREY KIM)/BI

((COREY(W)KIM)/BI)280 COREY/AB456 KIM/AB

3 (COREY KIM)/AB((COREY(W)KIM)/AB)

L2 5 (COREY KIM)/BI,AB

Figure 7. Computer search of CA for Corey-Kim reaction. (Repro-duced with permission of American Chemical Society.)

L2 ANSWER 1 OF 5COPYRIGHT (C) 1991 AMERICAN CHEMICAL SOCIETY

CA112(11):97704z Convenient synthesis of sulfur ylides by reaction ofactive methylene compounds with Corey-Kim reagent. Katayama,Sadarnu; Walanabe, Toshto; Yamauchi, Masashige (Fac. Pharm. Set.,Josai Univ., Sakado 350-02, Japan). Chem. Lett. (6), 973-6 (Eng)1989. CODEN: CMLTAG. ISSN: 0366-7022. OTHER SOURCES: CASREACT112:97704.

L2 ANSWER 2 OF 5COPYRIGHT (C) 1991 AMERICAN CHEMICAL SOCIETY

CA110(3) :23451b Synthesis of 1,3-dicarbonyl compounds by Ihe oxidationof 3-hydroxycarbonyl compounds with Corey-Kim reagent. Katayama,Sadarnu; Fukuda, Kinue; Watanabe, Toshio; Yamauchi, Masashige (Fac.Pharm. Sci., Josai Univ., Sakado 350-02, Japan). Synthesis (3),178-83 (Eng) 1988. CODEN: SYNTBF. ISSN: 0039-7881. OTHER SOURCES:CASREACT 110:23451.

Figure 8. Two of the references about the Corey-Kim reaction foundby computer search of CA. (Reproduced with permission of AmericanChemical Society.)

extensive information about the reaction and often includecomprehensive lists of relevant references. These books canbe identified by searching computerized versions of CA forthe name of the reaction and combining it with the wordBOOK. Also, computerized library catalogs can be accessedby keywords, which would permit identification of bookswhen the name reaction is part of the book title. Fourexamples are listed here:

Volume 68 Number 7 July 1991 555

7. Kharasch. Grignard Reactions of Nonmetallic Sub-stances

8. Fringelli and Taticchi. Dienes in the Diels-Alder Reac-tion

9. Olah. Friedel-Crafts and Related Reactions

10. Robinson. Fischer Indole Synthesis

Searching by Reaction TypeAnother group of questions asked by organic chemists

involve types of reactions. They may ask:

How does one carry out the halomethylation of an aromatic ring?or

What is the best way to carry out the reductive elimination ofbeta-haloesters, and what is the reaction stereochemistry?

Certain reference handbooks and books answer thesequestions very well.

Reaction Type: General Sources

11. House. Modern Synthetic ReactionsWritten for advanced undergraduates and beginning graduate

students.A rather detailed survey of many important synthetic methods

commonly used. An essential reference book for all new syn-thetic chemists.

Examples of chapters: Metal hydride reduction, oxidation, hal-ogenation, alkylation, aldol condensation, acylation. How-ever, some important reactions, such as the Diels-Alderreaction and Claisen rearrangement are not discussed; in-stead, readers are referred to other sources.

Information provided: reaction mechanism, stereochemistry,reaction conditions, examples of the reaction. For detailedexperimental procedures, readers are referred to journal ar-

ticles and other handbooks. Multiple references to the same

reaction are usually provided.An extensive subject index provides quick access to informa-

tion, for example, on acylation of esters, bromination of car-

boxylic acids, or hydroboration of enamines.

12. Carruthers. Some Modern Methods of Organic Syn-thesisAimed at advanced undergraduates and beginning graduate

students.Updates and complements House (no. 11); covers many reac-

tions not included in House, but in less detail.Provides the most important features of reactions.Chapters cover: formation of carbon-carbon single bonds and

double bonds, synthetic applications of organoboranes andorganosilanes, oxidation and reduction, reactions at un-

activated C-H bonds, and the Diels-Alder and related reac-

tions.Information such as oxidation of alcohols or catalytic hydrogen-

ation can be found readily in the rather detailed subject index.

13. Larock. Comprehensive Organic TransformationsAlthough the primary organization is by functional groups

being synthesized, each section is subdivided by major reac-

tion types, such as reduction, oxidation, alkylation, substitu-tion, elimination, coupling, halogenation, isomerization, etc.In some ways, this is an updated version of Wagner and Zook,Synthetic Organic Chemistry.

Focus is on major preparative reactions that are general inscope and on literature references in primary journals. It isnot exhaustive and specialized reactions are often not in-cluded.

Review articles are often listed at the beginning of sections,such as under Dehydrogenation of Alkenes.

The chapter on synthesis of alkenes has sections on theirpreparation by isomerization, elimination, alkylidenation ofcarbonyl compounds, metal-promoted coupling reactions, etc.

To locate information on preparation of alkenes by eliminationreactions, check the detailed table of contents of the Alkeneschapter under “Elimination”. More than 50 specific types ofelimination reactions, often based on different functionalgroup transformations, are listed. One can readily identify therelevant pages by selecting the type of elimination reactionrequired by the experiment. For example, if one’s reactioninvolves amine oxides, the information in Figure 9 would berelevant. The reaction scheme is shown, along with threemajorreferences to Journal ofthe American Chemical Society,Organic Reactions, and Organic Syntheses.

9. Amine Oxides (Cope Elimination)

o

H NR,

II ^ ^

JACS SI 2799 (1959); 1081039 (1986)Org Rxs 11 361 (1960) (review)Org Syn Coll Vot 4 612 (1963)

Figure 9. Entry from Larock, Comprehensive Organic Transforma-

14. Fieser. Reagents for Organic SynthesisThe long-time premier source for information about reagents.

The first and most extensive volume was published in 1967.Thirteen volumes have appeared since then in this continuingseries.

Entries list reaction scheme, along with brief, concise com-

ments about preferred methods of preparation. Referencesare given for journal articles that provide necessary experi-mental details.

Each volume includes an index of reagents according to reactiontype. A check under “Oxidation, Reagents” lists all oxidationreagents discussed in that volume.

A new Collective Index for volumes 1-12 (1990) includes a more

detailed “Type of Reaction Index” that permits precise selec-tion of reagent. To find information on “Oxidation Reactions”,scan the twelve pages devoted to this topic for the specific typeof oxidation reaction needed. For example, the subheadingALCOHOLS RCHO, R2CO lists two pages of reagents. Onecan easily locate the chromium reagents group and select theentry for “Potassium chromate, 9, 357”. The entry on p. 357of volume 9 is shown in Figure 10. Reference 13 refers tojournal article by D. Landini, F. Montanari and F. Rolla whichwas published in Synthesis, p. 134 (1979).

Oxidation of alcohols." Primary and secondary alcohols can be oxidized to

aldehydes and ketones, respectively, by potassium chromate and sulfuric acid in a

two-phase system (CHC13-H30) in the presence of tetra-rt-butyl ammonium hydro-gen sulfate as catalyst. The method is particularly useful for oxidation of primary

C.H.i.NHSO,

3RCH,OH + 2K2CrO4 + 5H3S04-—-* 3RCHO + 2K3S04 + Cr3lS04l3 + 8H30

alcohols, since aldehydes are not oxidized further to carboxylic acids under theseconditions. However, yields are low with water-soluble alcohols. With other alcohols

yields of aldehydes as high as 90% can be achieved. The method is suitable foroxidation of allylic alcohols and for acid-labile alcohols.

Figure 10. Entry from Fieser, Reagents for Organic Synthesis, v. 9(Reproduced with permission of Wiley)


15. Organic ReactionsMentioned also as a source for name reactions (see no. 5 above)Contains extensive review chapters which cover:

• reaction mechanism• scope and limitations of the reaction• experimental conditions and techniques• related synthetic processes• several detailed experimental procedures that illustrate

the reaction• tables listing all examples of the reaction with a com-

prehensive list of references to the original journal articles

To locate relevant chapters, check the cumulative subject indexin the most recent volume. For example, the index for volumes1-39 is found at the back of volume 39. A chapter on rear-

rangement of vinylcyclopropane to cyclopentene is found involume 33, chapter 2 by looking under Rearrangement. This90-page article includes a comprehensive table that listsstarting materials, products and yields, reaction conditions,and refers to the 228-article bibliography.

16. Organic SynthesesPublished annually since 1921.Gives proven procedures for the synthesis of individual organic

compounds.Each synthesis has been checked and reproduced in a second

laboratory before publication.Provides full experimental details of each synthesis.Collective volumes are available that revise and update the

information published in the annual volumes:v. 1-9 revised as Collective Volume 1 (1932)v. 10-19 revised as Collective Volume 2 (1943)v. 20-29 revised as Collective Volume 3 (1955)v. 30-39 revised as Collective Volume 4 (1963)v. 40-49 revised as Collective Volume 5 (1973)Separate volume of Cumulative Indices for Collective Vol-umes 1-5

v. 50-59 revised as Collective Volume 6 (1988)v. 60-64 revised as Collective Volume 7 (1990)The Concordance Index that appears in the last severalCollective Index Volumes lists the annual volume and pagenumber where each procedure first appeared. This corre-

lation is important because bibliographic references oftenrefer to annual volumes, whereas the Collective Volumepreparations are updated and therefore preferred.

Locating a desired procedure by reaction type can be accom-

plished in two ways:1. Check the “Type of Reaction Index” in the most recent

volumes and work back in time. This index has becomequite detailed in recent volumes, which is helpful for highlyspeeificquestions. Begin with the most recent index in theannual volumes (i.e., v. 68 that includes an index forvolumes 65-68), followed by the Collective Volume 7, then6 and back as far as appropriate.

To find recent references to preparation of cyclobutanoneby oxidation of an alcohol, check the “Oxidation” entry inthe “Type of Reaction Index” in Collective Volume 7. Oneof the choices is shown in Figure 11.

Selection of the cyclobutanone entry leads to the four-

IA Halomethyletion of Organic Compounds.................................... 2

lAa, Halomethylation of Activated Carbon Atoms...................">C~H -- -^C-CHiX.......... 3

IAb, Halomethylation of Aromatic Compounds.....................Ar-H--* Ar-CH2X ....... 4

I Ac, Halomethylation of Acyl Halides........................-co-x --- -co-ch2x........ 10

Figure 13. Table-of-contents from Mathieu, Formation of C-C Bonds, v.1, showing core reaction schemes. (Reproduced with permission ofThieme.)

CHOH C=0

[MnOj/C] 3-Butyroyl-l-niethylpyrrole,102

[Cr03/H2C204] Cyclobutanone, 114

[Cr03] 3,3-Dimethyl-cis'bicy-clo [3.2.0]heptan-2-one, 177

[(COCl)j/DMSOJ Geranial, 258

Figure 11. Entry from Organic Syntheses, Type of Reaction Index{Reproduced with permission of Wiley)

page experimental details of its preparation, along withcomments on its uses. A 22-article bibliography leads torelated procedures.

2. A Reaction Guide, published in 1991, summarizes instructural format all procedures published in volumes1-68.

Procedures are organized by 11 broad classes of reactiontypes, which, together with the highly visual structureformat, permit rapid scanning of reaction categories.The eleven classes include: addition, annulation, C-C bondformation, cleavage, elimination, oxidation, protection/deprotection, rearrangement, reduction, substitution, andmiscellaneous.

To use, check the Table of Contents for “Oxidation”. Sixbroad categories of oxidation reactions are listed: hetero-atom, epoxidation, halogenation, chromium reagents,manganese reagents, and general.

The 10 pages of chromium reagent entries are arrangedchronologically by Collective Volume numbers. The pagescan be scanned quickly to find the same synthesis as in the“Type of Reaction Index” above. The reaction scheme as

shown in Figure 12 focuses on the reaction site, whichfacilitates generic browsing. For full experimental details,one is referred to Organic Syntheses Collective Volume 7

p. 114 and Organic Syntheses Volume 60 p. 20.

Oxidation - Chromium Reagents

OS.CV7. 114(1990); 60, 20(1981)

OH

O'2Cr03

2 (COOH)26H*

h2o10.15 °C

Figure 12. Entry from Organic Syntheses, Reaction Guide (Repro-duced with permission of Wifey.)


IA Halomethylation

I Ab, Ar-H -* Ar —CHZX Halomethylation of Aromatic Compounds

®-H * (HCHO)„ . HCI„, 0-CH,-a

CHl CHj

* CH30-CHz-CI

CHjCHj

CHj CHj

^^-CHj-CICHj CH3

59V*

(HCHOJ„2nCI2, 5QCI2j HCl, CClt

10-20 hr 125- 30“!

CHj

CI-CH2

66 “A

IHCHOIn H3POt.CH3COOH,HClconeOh r 180-85“!

CH3-CI

1 G. Grassi, C.Maselli, Gazz. Chim. Ital. 28 II. 477 (1898)2R. C.Fuson, C.Fi. McKeever, Org. Reactions 1. 63 (1942).3G.A.OIah, Friedel Crafts and Related Reactions Vol II.

Part 2, p. 659, J. Wiley 81 Sons, New York 1964

Since 1898, halomethylation of aromatic compoundshas been the subject of a number of investigations, inparticular owing to the high reactivity of halogenswhich facilitates syntheses of numerous derivatives'"1.

Halomethylation of Aromatic Hydrocarbons

g Halomethylation of aromatic hydrocarbons is per-formed according to the Blanc procedure1 makinguse of aqueous formaldehyde or paraformaldehyde,respectively, together with hydrochloric acid and zincchloride.

Chloromethylation may also be achieved by treating7 the corresponding aromatic compound with chloro-

methyl ether in carbon tetrachloride or carbon disul-fide in the presence of tin(IV)chloride as shown fordurene6 7.

This process has been subjected to a variety of modifications reported in literature.

The Blanc procedure has been modified by em8 ploying zinc chloride together with thionyl chloride

eliminating water and thus leading to a considerablyhigher yield of halomethylated compound, particular-ly in the polycondensation reactions*.

In the case of naphthalene, a mineral acid, e g. phos-9 phoric acid9 has been substituted for zinc chloride.

4J.Schreiber, Chem. Usty 55. 282 (1961): C.A. 55. 19738(1961).

'G.Blanc. Bull. Soc. Chim, France [4] 33, 313 (1923)6 M.Sommelet. Compt. Rend. 157, 1443 (1913).’R.C.Fuson- H.O House L.R.Melby, J.Am Chem.Soc 755952 (1953).

‘G.Drechsler, J. Prakl. Chem. [4] 19, 283 (1963).’O. Grummitt, A.Buck, Org. Syntheses, Coll. Vol III. 196(1955).

Figure 14. Typical halomethylation reactions from Mathieu, Formation ofC-C Bonds, v.1. (Reproduced with permission of Thieme.)

17. Mathieu. Formation ofC-C Bonds

Consists of three volumes that describe classical reactions thatinvolve formation of specific types of carbon-carbon bonds.

v. 1 Introduction of a Functional Carbon Atom

v. 2 Introduction of a Carbon Chain or an Aromatic Ringv. 3 Introduction of an Alpha-Functional Carbon Chain

Not all reaction types are covered.

A detailed table of contents with core reaction schemes make iteasy to identify relevant pages. The reaction site is printed inred (on original pages).

The sections consist of reaction schemes for typical reactions,with brief comments and journal references. Charts of typicalsyntheses that utilize the reactions include: starting materi-als, reagents and solvents, reaction products, yields, andjournal references for additional details.

To find examples of halomethylation of aromatic compounds:•Select volume 1 and scan its table of contents to locate the

chapter on “Halomethylation of Organic Compounds” (seeFig. 13). Turn to the section on aromatic compounds thatbegins on page 4.

Figure 14 shows the reaction schemes of typical reac-

tions, with comments about the reaction and references tomajor articles. Figure 15 lists typical syntheses of aromaticcompounds that utilize the halomethylation reaction.

18. Annual Reports in Organic SynthesisAn annual review of synthetically useful information that

groups related reactions together. Fast scanning is facilitatedby use of structures and reaction schemes. A disadvantage isthat each annual volume must be scanned, and there is no

cumulative index.References to journal articles are listed, along with selective

experimental notes.An excellent source for helping chemists stay up-to-date and to

quickly scan for relevant reactions as needed.The detailed table of contents serves in place of an index.To check for epoxidation of alkenes, first check the table of

contents under Oxidations. Then turn to page 250 for concisedescriptions of epoxidations of C-C multiple bonds. Two of theentries are shown in Figure 16.

19. March. Advanced Organic ChemistryMentioned also as a source for descriptions of name reactions

(see no. 2 above).A reference source for students and professional chemists.Part 2 is organized by reaction types, with chapters on aromatic

nucleophilic and electrophilic substitution, aliphatic nucle-ophilic and electrophilic substitution, free radical substitu-tion, eliminations, rearrangements, oxidations, reductions,additions to carbon-carbon multiple bonds, and additions tocarbon-hetero multiple bonds.


I Ab, Halomethylation of Aromatic Compounds

' G.Blanc. Bull.Soc. Chim. France [4] 33, 313 (1923).2 G. Drechs/er, J. Prakt. Chem. [4] 19, 283 (1963).3i.Shahak. £ D Bergmann J Chem Soc [C] 1966, 1005.4B. C.Fuson, H. 0. House, L. R.Melby, J. Am. Chem. Soc. 75,

5952 (1953).5 M. S. Newman, J. R. Le Blanc. H. A. Karnes. G.Axelrad, J. Am.

Chem. Soc. 86. 868 (1964).6O.Grummitt. A.Buck. Org.Syntheses. Coll.Vol III. 195

(1955).1G Lock, R.Schneider. Chem. Ber. 91, 1770 (1958).

Figure 15. Typical halomethylated aromatic syntheses from Mathieu, Formation ofC-C Bonds, v. 1 (Reproduced with permission of Thieme)

Discusses scope of reactions, limitations, and mechanisms, andprovides extensive references to journal articles for detailedexperimental procedures.

Includes a detailed subject index which permits rapid locationof reactions of groups of substances, such as hydrolysis ofamides, of cyclopropanes, of enamines, etc.

20. Carey and Sundberg.Advanced Organic Chemistry.Part B.

Mentioned also as a source for descriptions of name reactions(see no. 3 above)

A comprehensive textbook for advanced undergraduates andgraduate students, which professional chemists will use as a

reference manual.Describes synthetically useful reactions and their applications

in an easy to follow format using extensive reaction diagrams,with references to journal articles and handbooks.

Includes extensive chapters on oxidations, aromatic substitu-tion, cycloadditions, reduction, electrophilic additions, alkyla-tion, and reactions involving metals.

Many reaction mechanisms are given.The detailed table of contents helps one readily locate the pages

for oxidation of alcohols.To use the subject index, look under the type of compound first.

So, check under alcohols, then oxidation, to find the pagesabout oxidation of alcohols.

Figure 16. Two entries from 1989 Annual Reports in Organic Synthe- Each chapter concludes with a selected list of general referencessis. (Reproduced with permission of Academic.) ancj practice questions.


Figure 17. Example of a retrosynthetically derived multistep sequence synthesisfrom Corey and Cheng, The Logic of Chemical Synthesis. (Reproduced withpermission of Wiley.)21. Corey and Cheng. Logic of Chemical Synthesis

Describes the synthon based strategic analysis of syntheticdesign pioneered by Corey and coworkers.

An advanced level book that describes the principles of retro-synthetic analysis and transform- and structure-based strat-egies.

Its special values are in visual synopses of actual syntheses thatillustrate these principles and as a useful catalog of multistepsyntheses in the literature.

An example of this process applied to the synthesis of a

sesquiterpenoid, specifically alpha-caryophyllene alcohol, isshown in Figure 17

22. Comprehensive Organic Synthesis (scheduled for pub-lication late in 1991. Information taken from advancebrochure.)A reference guide for students and professional chemists.Each of the eight volumes describe types of synthetic reactions

by reaction type. The volumes will cover: additions to C-Xpi-bonds, carbon-carbon sigma bonds, additions to and sub-stitutions at C-C pi-bonds, combining C-C pi bonds, hetero-atom manipulation, oxidation, and reduction. Volume 9 willinclude cumulative author and subject indexes.

Each volume is edited by an expert, has its own author andsubject index, and includes chapters written by experts.

23. Comprehensive Organic ChemistryA reference guide for students and professional chemists.Five volumes describe the properties and reactions of the im-

portant classes of organic compounds. Within each class ofcompounds, such as alcohols, there is an extensive discussionof major reactions of alcohols.

Volume 6 includes several indexes, one of which is Reac-tion Index.

To locate oxidation reactions of alcohols, check the Reac-tion Index under Oxidation, then Alcohols, to find the 10pages in Volume 1 that describe in some detail oxidationof alcohols to carbonyl compounds. Extensive referencesto journal articles and reference handbooks provide ac-

cess to experimental details. The Index also refers toentries for brief comments about oxidation reactions ofalcohols.

To locate oxidation reactions used to synthesize sub-stances, check the Subject Index under the type of sub-stance to be synthesized, such as carbonyl compounds,aldehydes, and ketones. This is a less effective search,unless one generalizes and looks for preparation of car-

bonyl compounds.

Reaction Type: Specific Sources

Some reactions, such as oxidation, reduction,cycloaddition, and hydroboration are sufficientlyimportant that books are written about them.Other books provide extensive chapters about re-action types. A highly selective, but representa-tive, list of books is provided as references 25-36on the chart at the end of the article.

Practice Questions1. Find experimental procedures to efficiently

carry out the Nef Reaction on simple aliphaticstarting materials.

Answer: The Nef Reaction is found in Mundy’sName Reactions and Reagents in Organic Reactions, p.154-55. The general reaction scheme and mechanismare provided, as well as areference to March’s AdvancedOrganic Chemistry and one example of the reaction withaliphatic compounds. If this information is not adequate,check the cumulative index in the latest volume of

Organic Reactions. There one is referred to the Nef Reactionchapter in volume 38, p. 655-792. This is an exhaustive discus-sion about the Nef Reaction. Eight experimental procedures,including several for aliphatic substances, are described on

pages before the tabular data. The 349 references lead to reviewarticles as well as specific applications.

2. What is the product of the photosensitized oxygenationof alkenes? Is the photosensitized oxygenation of methy-lene cycloalkanes a preparatively useful synthetic reac-

tion?

Answer: The March and House textbooks both have de-

scriptions of photooxygenation of alkenes. These pages are

found by checking under the topics photooxidation or photosen-sitization in the indexes. Note that one should be alert tochecking various terms that describe the topic. Photooxygena-tion is another possible term. This insight is used when check-ing the cumulative index of Organic Reactions. Under“Photooxygenation of olefins”, one is referred to Organic Reac-tions, volume 20, chapter two. This 199 page article, “SensitizedPhotooxygenation of Olefins”, describes the reaction in detailand specifically answers the methylene cycloalkanes question.The tabular chart lists the structure, which permits rapidscanning to identify methylenecycloaikanes, and the percent-age yield, along with reaction conditions, products if any, andthe journal reference. Other general information about thereaction is found in Comprehensive Organic Chemistry. ItsReaction Index includes entries for “Photo oxygenation reviews,of olefins".

3. What are some uses of the intramolecular ene reactionin natural products synthesis?


Answer: The Carey and Sundberg, March, and Carrutherstextbooks all provide some information about the ene reaction,with the Carruthers coverage the most extensive. This infor-mation is located by checking the index of each book under “EneReaction”. The nine pages in Carruthers include paragraphs on

the potential of intramolecular ene reactions for synthesis ofnatural products. A check of Larock’s table of contents under

Information Sources—Organic Chemistry

Information on Reactions by Name Reaction

General References

1. Mundy. Name Reactions and Reagents in Organic Chemis-try2. March. Advanced Organic Chemistry, Part 2

3. Carey & Sundberg. Advanced Organic Chemistry, Part B.4. Surrey. Name Reactions in Organic Chemistry5. Organic Reactions6. Chemical Abstracts

Specific References

7. Kharasch. Grignard Reactions of Nonmetallic Substances8. Fringuelli & Taticchi. Dienes in the Diels-Alder Reaction9. Olah. Friedel-Crafts and Related Reactions

10. Robinson. Fischer Indole Synthesis

Information on Reactions by Reaction Type

General References

11. House. Modern Synthetic Reactions12. Carruthers. Some Modern Methods of Organic Synthesis13. Larock. Comprehensive Organic Transformations14. Fieser. Reagents for Organic Synthesis15. Organic Reactions16. Organic Syntheses17. Mathieu. Formation ofC-C Bonds18. Annual Reports in Organic Synthesis19. March. Advanced Organic Chemistry20. Carey and Sundberg. Advanced Organic Chemistry21. Corey and Chang. The Logic of Chemical Synthesis22. Comprehensive Organic Synthesis23. Comprehensive Organic Chemistry

Specific References

24. ApSimon. The Total Synthesis of Natural Products25. Hanessian. Total Synthesis of Natural Products: The Chi-

ron Approach26. Morrison. Asymmetric Synthesis27. Carruthers. Cycloaddition Reactions in Organic Synthesis28. Brown. Hydroboration29. Giese. Radicals in Organic Synthesis30. Harrington. Transition Metals in Total Synthesis31. Gaylord. Reduction with Complex Metal Hydrides

32. Augustine. Oxidation33. Fried and Edwards. Organic Reactions in Steroid Chemis-

try34. Nogradi. Stereoselective Synthesis35. Hase. Umpoled Synthons

alkenes locates an entry for ene reaction that includes a refer-ence to intramolecular reactions in Angewandte Chemie, Inter-national Edition in English, v. 17, 1978. This article by W.Oppolzer and V. Snieckus, “Intramolecular Ene Reactions inOrganic Synthesis”, fully answers the question.

Bibliographic Information to Accompany the ChartAnnual Reports in Organic Synthesis; Academic: New York,

1970-ApSimon, J. The Total Synthesis of Natural Products, 7 vols.;

Wiley: New York, 1973-88.Augustine, R. Oxidation: Techniques and Applications in Or-

ganic Chemistry, 2 vols.; Dekker: New York, 1969-71.Brown, H. C. Hydroboration; Benjamin/Cummings: Reading,

MA, 1980.Carey, F. A.; Sundberg, R.J. Advanced Organic Chemistry, 2

vols., 3rd ed.; Plenum: New York, 1990.Carruthers, W. Cycloaddition Reactions in Organic Synthesis;

Pergamon: New York, 1990.Carruthers, W. Some Modern Methods of Organic Synthesis,

3rd ed.; Cambridge University: New York, 1986.Chemical Abstracts; Chemical Abstracts Service: Columbus,

OH, 1907-Comprehensive Organic Chemistry: The Synthesis and Reac-

tions of Organic Compounds, 6 vols.; Pergamon: New York,1979.

Comprehensive Organic Synthesis: Selectivity, Strategy andEfficiency in Modern Organic Chemistry, 9 vols.; Pergamon:New York, 1991.

Corey, E. J.; Cheng, X. M. The Logic of Chemical Synthesis;Wiley: New York, 1989.

Fieser, L. F. Reagents for Organic Synthesis; Wiley: New York,1967-

Fried, J.; Edwards, J. A., Eds. Organic Reactions in SteroidChemistry; Van Nostrand Reinhold: New York, 1972.

Fringuelli, F.; Taticchi, A. Dienes in the Diels-Alder Reaction;Wiley: New York, 1990.

Gaylord, N. Reduction with Complex Metal Hydrides; Intersci-ence: New York, 1956.

Giese, B. Radicals in Organic Synthesis: Formation of Carbon-Carbon Bonds; Pergamon: New York, 1986.

Hanessian, S. Total Synthesis of Natural Products: The ChironApproach; Pergamon: New York, 1983.

Harrington, P.J. Transition Metals in Total Synthesis; Wiley:New York, 1990.

Hase, T. A. Umpoled Synthons: A Survey of Sources and Usesin Synthesis; Wiley: New York, 1987.

House, H. O. Modern Synthetic Reactions, 2nd ed; Benjamin:Menlo Park, CA, 1972.

Kharasch, M. S.; Reinmuth, O. Grignard Reactions of Nonme-tallic Substances; Prentice-Hall: New York, 1954.

Larock, R. C. Comprehensive Organic Transformations: AGuide to Functional Group Preparations; VCH: New York,1989.

March, J. Advanced Organic Chemistry: Reactions, Mecha-nisms and Structure, 3rd ed.; Wiley: New York, 1985; 2 vols.

Mathieu, J.; Weill-Raynal, J .Formation ofC-C Bonds; Thieme:Stuttgart, 1973-

Morrison, J. D., Ed. Asymmetric Synthesis, 5 vols.; Academic:New York, 1983-85.

Mundy, B. P.; Ellerd, M. G. Name Reactions and Reagents inOrganic Synthesis; Wiley: New York: 1988.

Nogradi, M. Stereoselective Synthesis; VCH: New York, 1987.Olah, G. A. Friedel-Crafts and Related Reactions, 6 pts. in 4

vols.; Interscience: New York, 1963-65.Organic Reactions; Wiley: New York, 1942-Organic Syntheses; Wiley: New York, 1960-Robinson, B. Fischer Indole Synthesis; Wiley: New York, 1982.Surrey, A. R. Name Reactions in Organic Chemistry, 2nd ed.;

Academic: New York, 1961.


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