Molecular orbital model of regioselective free-radical aromatic substitution View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

1988-07

AUTHORS

S. V. Volovik, G. G. Dyadyusha, V. I. Staninets

ABSTRACT

Within the framework of the one-electron MO perturbation method, a simple qualitative model has been developed for positional selectivity of free-radical substitution in the aromatic ring, with which the basic regiochemical trends can be predicted. The dominant trends in regioselectivity of homolytic aromatic substitution are determined by the polar (“philic”) character of the attacking radical and the symmetry of the regiocontrolling MOs are the frontier orbitals and the next (second) HOMOs and LUMOs. In situations in which the attacking radical is distinctly polar relative to the aromatic substrate (where the radical has a nucleophilic or electrophilic character) and the regiocontrolling MO is an orbital of the b1 type (C2v symmetry), ipso attack is possible, with subsequent ipso-ortho rearrangement. In the case of an ambiphilic attacking radical, this probability is very low. The effectiveness of the approach is illustrated in examples of the interaction of various free radicals with monosubstituted benzenes. In addition, other applications of the model are discussed. More... »

PAGES

380-386

References to SciGraph publications

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/bf00536354

DOI

http://dx.doi.org/10.1007/bf00536354

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1027083918


Indexing Status Check whether this publication has been indexed by Scopus and Web Of Science using the SN Indexing Status Tool
Incoming Citations Browse incoming citations for this publication using opencitations.net

JSON-LD is the canonical representation for SciGraph data.

TIP: You can open this SciGraph record using an external JSON-LD service: JSON-LD Playground Google SDTT

[
  {
    "@context": "https://springernature.github.io/scigraph/jsonld/sgcontext.json", 
    "about": [
      {
        "id": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/0305", 
        "inDefinedTermSet": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/", 
        "name": "Organic Chemistry", 
        "type": "DefinedTerm"
      }, 
      {
        "id": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/03", 
        "inDefinedTermSet": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/", 
        "name": "Chemical Sciences", 
        "type": "DefinedTerm"
      }
    ], 
    "author": [
      {
        "affiliation": {
          "alternateName": "Institute of Organic Chemistry", 
          "id": "https://www.grid.ac/institutes/grid.464621.3", 
          "name": [
            "Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Volovik", 
        "givenName": "S. V.", 
        "id": "sg:person.012711207717.76", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.012711207717.76"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Institute of Organic Chemistry", 
          "id": "https://www.grid.ac/institutes/grid.464621.3", 
          "name": [
            "Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Dyadyusha", 
        "givenName": "G. G.", 
        "id": "sg:person.07614144765.30", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.07614144765.30"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Institute of Organic Chemistry", 
          "id": "https://www.grid.ac/institutes/grid.464621.3", 
          "name": [
            "Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Staninets", 
        "givenName": "V. I.", 
        "id": "sg:person.016653667731.06", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.016653667731.06"
        ], 
        "type": "Person"
      }
    ], 
    "citation": [
      {
        "id": "https://doi.org/10.1139/v70-169", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1000782111"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/bf00522538", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1003692533", 
          "https://doi.org/10.1007/bf00522538"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/bf00522538", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1003692533", 
          "https://doi.org/10.1007/bf00522538"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/p19720000570", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1007321647"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/bf00534572", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1015396688", 
          "https://doi.org/10.1007/bf00534572"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/bf00534572", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1015396688", 
          "https://doi.org/10.1007/bf00534572"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1246/bcsj.47.2563", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1020171688"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/j29680000048", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1022137033"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/j29680000022", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1023626272"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1246/bcsj.43.1131", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1026184039"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://app.dimensions.ai/details/publication/pub.1027046653", 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://app.dimensions.ai/details/publication/pub.1027046653", 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/jr9560001463", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1046424944"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/978-3-642-61917-5", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1047336892", 
          "https://doi.org/10.1007/978-3-642-61917-5"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "sg:pub.10.1007/978-3-642-61917-5", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1047336892", 
          "https://doi.org/10.1007/978-3-642-61917-5"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1039/j29700001683", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1047939441"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ar50129a004", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055151384"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/j100624a005", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055674380"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ja00439a014", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055732615"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ja00791a020", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055748200"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ja00880a038", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055754662"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/ja00974a035", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055758244"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1021/jo00902a020", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1055990646"
        ], 
        "type": "CreativeWork"
      }, 
      {
        "id": "https://doi.org/10.1063/1.1727954", 
        "sameAs": [
          "https://app.dimensions.ai/details/publication/pub.1057794497"
        ], 
        "type": "CreativeWork"
      }
    ], 
    "datePublished": "1988-07", 
    "datePublishedReg": "1988-07-01", 
    "description": "Within the framework of the one-electron MO perturbation method, a simple qualitative model has been developed for positional selectivity of free-radical substitution in the aromatic ring, with which the basic regiochemical trends can be predicted. The dominant trends in regioselectivity of homolytic aromatic substitution are determined by the polar (\u201cphilic\u201d) character of the attacking radical and the symmetry of the regiocontrolling MOs are the frontier orbitals and the next (second) HOMOs and LUMOs. In situations in which the attacking radical is distinctly polar relative to the aromatic substrate (where the radical has a nucleophilic or electrophilic character) and the regiocontrolling MO is an orbital of the b1 type (C2v symmetry), ipso attack is possible, with subsequent ipso-ortho rearrangement. In the case of an ambiphilic attacking radical, this probability is very low. The effectiveness of the approach is illustrated in examples of the interaction of various free radicals with monosubstituted benzenes. In addition, other applications of the model are discussed.", 
    "genre": "research_article", 
    "id": "sg:pub.10.1007/bf00536354", 
    "inLanguage": [
      "en"
    ], 
    "isAccessibleForFree": false, 
    "isPartOf": [
      {
        "id": "sg:journal.1010993", 
        "issn": [
          "0040-5760", 
          "1573-935X"
        ], 
        "name": "Theoretical and Experimental Chemistry", 
        "type": "Periodical"
      }, 
      {
        "issueNumber": "4", 
        "type": "PublicationIssue"
      }, 
      {
        "type": "PublicationVolume", 
        "volumeNumber": "23"
      }
    ], 
    "name": "Molecular orbital model of regioselective free-radical aromatic substitution", 
    "pagination": "380-386", 
    "productId": [
      {
        "name": "doi", 
        "type": "PropertyValue", 
        "value": [
          "10.1007/bf00536354"
        ]
      }, 
      {
        "name": "readcube_id", 
        "type": "PropertyValue", 
        "value": [
          "8104e5434ebf32d28754d2fd69dd8cb55c4768a8ea94bc531e8965003bb55b0d"
        ]
      }, 
      {
        "name": "dimensions_id", 
        "type": "PropertyValue", 
        "value": [
          "pub.1027083918"
        ]
      }
    ], 
    "sameAs": [
      "https://doi.org/10.1007/bf00536354", 
      "https://app.dimensions.ai/details/publication/pub.1027083918"
    ], 
    "sdDataset": "articles", 
    "sdDatePublished": "2019-04-15T08:58", 
    "sdLicense": "https://scigraph.springernature.com/explorer/license/", 
    "sdPublisher": {
      "name": "Springer Nature - SN SciGraph project", 
      "type": "Organization"
    }, 
    "sdSource": "s3://com-uberresearch-data-dimensions-target-20181106-alternative/cleanup/v134/2549eaecd7973599484d7c17b260dba0a4ecb94b/merge/v9/a6c9fde33151104705d4d7ff012ea9563521a3ce/jats-lookup/v90/0000000375_0000000375/records_91428_00000000.jsonl", 
    "type": "ScholarlyArticle", 
    "url": "http://link.springer.com/10.1007%2FBF00536354"
  }
]
 

Download the RDF metadata as:  json-ld nt turtle xml License info

HOW TO GET THIS DATA PROGRAMMATICALLY:

JSON-LD is a popular format for linked data which is fully compatible with JSON.

curl -H 'Accept: application/ld+json' 'https://scigraph.springernature.com/pub.10.1007/bf00536354'

N-Triples is a line-based linked data format ideal for batch operations.

curl -H 'Accept: application/n-triples' 'https://scigraph.springernature.com/pub.10.1007/bf00536354'

Turtle is a human-readable linked data format.

curl -H 'Accept: text/turtle' 'https://scigraph.springernature.com/pub.10.1007/bf00536354'

RDF/XML is a standard XML format for linked data.

curl -H 'Accept: application/rdf+xml' 'https://scigraph.springernature.com/pub.10.1007/bf00536354'


 

This table displays all metadata directly associated to this object as RDF triples.

137 TRIPLES      21 PREDICATES      47 URIs      19 LITERALS      7 BLANK NODES

Subject Predicate Object
1 sg:pub.10.1007/bf00536354 schema:about anzsrc-for:03
2 anzsrc-for:0305
3 schema:author N0bbb2c269e0c4bd39a2f8e62aa7fa33f
4 schema:citation sg:pub.10.1007/978-3-642-61917-5
5 sg:pub.10.1007/bf00522538
6 sg:pub.10.1007/bf00534572
7 https://app.dimensions.ai/details/publication/pub.1027046653
8 https://doi.org/10.1021/ar50129a004
9 https://doi.org/10.1021/j100624a005
10 https://doi.org/10.1021/ja00439a014
11 https://doi.org/10.1021/ja00791a020
12 https://doi.org/10.1021/ja00880a038
13 https://doi.org/10.1021/ja00974a035
14 https://doi.org/10.1021/jo00902a020
15 https://doi.org/10.1039/j29680000022
16 https://doi.org/10.1039/j29680000048
17 https://doi.org/10.1039/j29700001683
18 https://doi.org/10.1039/jr9560001463
19 https://doi.org/10.1039/p19720000570
20 https://doi.org/10.1063/1.1727954
21 https://doi.org/10.1139/v70-169
22 https://doi.org/10.1246/bcsj.43.1131
23 https://doi.org/10.1246/bcsj.47.2563
24 schema:datePublished 1988-07
25 schema:datePublishedReg 1988-07-01
26 schema:description Within the framework of the one-electron MO perturbation method, a simple qualitative model has been developed for positional selectivity of free-radical substitution in the aromatic ring, with which the basic regiochemical trends can be predicted. The dominant trends in regioselectivity of homolytic aromatic substitution are determined by the polar (“philic”) character of the attacking radical and the symmetry of the regiocontrolling MOs are the frontier orbitals and the next (second) HOMOs and LUMOs. In situations in which the attacking radical is distinctly polar relative to the aromatic substrate (where the radical has a nucleophilic or electrophilic character) and the regiocontrolling MO is an orbital of the b1 type (C2v symmetry), ipso attack is possible, with subsequent ipso-ortho rearrangement. In the case of an ambiphilic attacking radical, this probability is very low. The effectiveness of the approach is illustrated in examples of the interaction of various free radicals with monosubstituted benzenes. In addition, other applications of the model are discussed.
27 schema:genre research_article
28 schema:inLanguage en
29 schema:isAccessibleForFree false
30 schema:isPartOf N3bf642f800a54617922d9ff85728ba2d
31 Nf48dcb9d00824a6cbf9aaa9587a7f8e9
32 sg:journal.1010993
33 schema:name Molecular orbital model of regioselective free-radical aromatic substitution
34 schema:pagination 380-386
35 schema:productId N38f1cd0eb4c148d5824c45e9e00b9eeb
36 N614abeb5f28a4257a45d1f662451ae2e
37 Nc5458b8d62784534bc14fbf199fa188e
38 schema:sameAs https://app.dimensions.ai/details/publication/pub.1027083918
39 https://doi.org/10.1007/bf00536354
40 schema:sdDatePublished 2019-04-15T08:58
41 schema:sdLicense https://scigraph.springernature.com/explorer/license/
42 schema:sdPublisher N24998ac2c1d54113957cee3ceb5f6e35
43 schema:url http://link.springer.com/10.1007%2FBF00536354
44 sgo:license sg:explorer/license/
45 sgo:sdDataset articles
46 rdf:type schema:ScholarlyArticle
47 N0bbb2c269e0c4bd39a2f8e62aa7fa33f rdf:first sg:person.012711207717.76
48 rdf:rest N39239807e6a84dd285d9f17d7423a9f5
49 N0d876614d9c24d7094fd365e09b4f2b5 rdf:first sg:person.016653667731.06
50 rdf:rest rdf:nil
51 N24998ac2c1d54113957cee3ceb5f6e35 schema:name Springer Nature - SN SciGraph project
52 rdf:type schema:Organization
53 N38f1cd0eb4c148d5824c45e9e00b9eeb schema:name readcube_id
54 schema:value 8104e5434ebf32d28754d2fd69dd8cb55c4768a8ea94bc531e8965003bb55b0d
55 rdf:type schema:PropertyValue
56 N39239807e6a84dd285d9f17d7423a9f5 rdf:first sg:person.07614144765.30
57 rdf:rest N0d876614d9c24d7094fd365e09b4f2b5
58 N3bf642f800a54617922d9ff85728ba2d schema:volumeNumber 23
59 rdf:type schema:PublicationVolume
60 N614abeb5f28a4257a45d1f662451ae2e schema:name doi
61 schema:value 10.1007/bf00536354
62 rdf:type schema:PropertyValue
63 Nc5458b8d62784534bc14fbf199fa188e schema:name dimensions_id
64 schema:value pub.1027083918
65 rdf:type schema:PropertyValue
66 Nf48dcb9d00824a6cbf9aaa9587a7f8e9 schema:issueNumber 4
67 rdf:type schema:PublicationIssue
68 anzsrc-for:03 schema:inDefinedTermSet anzsrc-for:
69 schema:name Chemical Sciences
70 rdf:type schema:DefinedTerm
71 anzsrc-for:0305 schema:inDefinedTermSet anzsrc-for:
72 schema:name Organic Chemistry
73 rdf:type schema:DefinedTerm
74 sg:journal.1010993 schema:issn 0040-5760
75 1573-935X
76 schema:name Theoretical and Experimental Chemistry
77 rdf:type schema:Periodical
78 sg:person.012711207717.76 schema:affiliation https://www.grid.ac/institutes/grid.464621.3
79 schema:familyName Volovik
80 schema:givenName S. V.
81 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.012711207717.76
82 rdf:type schema:Person
83 sg:person.016653667731.06 schema:affiliation https://www.grid.ac/institutes/grid.464621.3
84 schema:familyName Staninets
85 schema:givenName V. I.
86 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.016653667731.06
87 rdf:type schema:Person
88 sg:person.07614144765.30 schema:affiliation https://www.grid.ac/institutes/grid.464621.3
89 schema:familyName Dyadyusha
90 schema:givenName G. G.
91 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.07614144765.30
92 rdf:type schema:Person
93 sg:pub.10.1007/978-3-642-61917-5 schema:sameAs https://app.dimensions.ai/details/publication/pub.1047336892
94 https://doi.org/10.1007/978-3-642-61917-5
95 rdf:type schema:CreativeWork
96 sg:pub.10.1007/bf00522538 schema:sameAs https://app.dimensions.ai/details/publication/pub.1003692533
97 https://doi.org/10.1007/bf00522538
98 rdf:type schema:CreativeWork
99 sg:pub.10.1007/bf00534572 schema:sameAs https://app.dimensions.ai/details/publication/pub.1015396688
100 https://doi.org/10.1007/bf00534572
101 rdf:type schema:CreativeWork
102 https://app.dimensions.ai/details/publication/pub.1027046653 schema:CreativeWork
103 https://doi.org/10.1021/ar50129a004 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055151384
104 rdf:type schema:CreativeWork
105 https://doi.org/10.1021/j100624a005 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055674380
106 rdf:type schema:CreativeWork
107 https://doi.org/10.1021/ja00439a014 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055732615
108 rdf:type schema:CreativeWork
109 https://doi.org/10.1021/ja00791a020 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055748200
110 rdf:type schema:CreativeWork
111 https://doi.org/10.1021/ja00880a038 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055754662
112 rdf:type schema:CreativeWork
113 https://doi.org/10.1021/ja00974a035 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055758244
114 rdf:type schema:CreativeWork
115 https://doi.org/10.1021/jo00902a020 schema:sameAs https://app.dimensions.ai/details/publication/pub.1055990646
116 rdf:type schema:CreativeWork
117 https://doi.org/10.1039/j29680000022 schema:sameAs https://app.dimensions.ai/details/publication/pub.1023626272
118 rdf:type schema:CreativeWork
119 https://doi.org/10.1039/j29680000048 schema:sameAs https://app.dimensions.ai/details/publication/pub.1022137033
120 rdf:type schema:CreativeWork
121 https://doi.org/10.1039/j29700001683 schema:sameAs https://app.dimensions.ai/details/publication/pub.1047939441
122 rdf:type schema:CreativeWork
123 https://doi.org/10.1039/jr9560001463 schema:sameAs https://app.dimensions.ai/details/publication/pub.1046424944
124 rdf:type schema:CreativeWork
125 https://doi.org/10.1039/p19720000570 schema:sameAs https://app.dimensions.ai/details/publication/pub.1007321647
126 rdf:type schema:CreativeWork
127 https://doi.org/10.1063/1.1727954 schema:sameAs https://app.dimensions.ai/details/publication/pub.1057794497
128 rdf:type schema:CreativeWork
129 https://doi.org/10.1139/v70-169 schema:sameAs https://app.dimensions.ai/details/publication/pub.1000782111
130 rdf:type schema:CreativeWork
131 https://doi.org/10.1246/bcsj.43.1131 schema:sameAs https://app.dimensions.ai/details/publication/pub.1026184039
132 rdf:type schema:CreativeWork
133 https://doi.org/10.1246/bcsj.47.2563 schema:sameAs https://app.dimensions.ai/details/publication/pub.1020171688
134 rdf:type schema:CreativeWork
135 https://www.grid.ac/institutes/grid.464621.3 schema:alternateName Institute of Organic Chemistry
136 schema:name Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev
137 rdf:type schema:Organization
 




Preview window. Press ESC to close (or click here)


...