Structures of oxidation products of 4,6-di-tert-butylpyrogallol View Full Text


Ontology type: schema:ScholarlyArticle     


Article Info

DATE

1999-01

AUTHORS

A. I. Shif, S. N. Lyubchenko, O. Ya. Borbulevych, O. V. Shishkin, K. A. Lyssenko, L. P. Olekhnovich

ABSTRACT

Oxidation of 4,6-di-tert-butylpyrogallol gave two dimeric products instead of the expected 4,6-di-tert-butyl-3-hydroxy-1,2-benzoquinone (2). It was established by X-ray diffraction analysis that the first product has the structure of tetra-tert-butyl-6, 10a-dihydroxy-1,2-dioxo-3,4a,7,9-1,2,4a, 10a-tetrahydrodibenzo-1,4-dioxine. From this it follows that compound 2 undergoes regio- and stereospecific dimerization according to the [2π+4π]-cycloaddition mechanism,viz, the hetero Diels—Alder reaction. The double intensities of the signals in the1H NMR spectrum are indicative of a symmetrical structure of the second product, 2,6,4′, 6′-tetra-tert-butyl-4,4′-dihyroxy-3,5,3′,5′-tetraoxo-4,4′-bi(cyclohexene), which is a racemate of enantiomers formed upon recombination (r+r orl+l) of the intermediate of oxidation of pyrogallol, namely, of ther,l-stereogenic 3,5-di-tert-butyl-1-hydroxy-2,6-dioxocyclohex-3-enyl radical. More... »

PAGES

139-146

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/bf02494416

DOI

http://dx.doi.org/10.1007/bf02494416

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1035289330


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/2008/03", 
        "inDefinedTermSet": "http://purl.org/au-research/vocabulary/anzsrc-for/2008/", 
        "name": "Chemical Sciences", 
        "type": "DefinedTerm"
      }
    ], 
    "author": [
      {
        "affiliation": {
          "alternateName": "Scientific Research Institute of Physical and Organic Chemistry at Rostov State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation", 
          "id": "http://www.grid.ac/institutes/grid.182798.d", 
          "name": [
            "Scientific Research Institute of Physical and Organic Chemistry at Rostov State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Shif", 
        "givenName": "A. I.", 
        "id": "sg:person.014520050323.79", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.014520050323.79"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Department of Chemistry, Rostov State University, 7 ul. Zorge, 344090, Rostov-on-Don, Russian Federation", 
          "id": "http://www.grid.ac/institutes/grid.182798.d", 
          "name": [
            "Department of Chemistry, Rostov State University, 7 ul. Zorge, 344090, Rostov-on-Don, Russian Federation"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Lyubchenko", 
        "givenName": "S. N.", 
        "id": "sg:person.010113170153.15", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.010113170153.15"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation", 
          "id": "http://www.grid.ac/institutes/grid.431939.5", 
          "name": [
            "A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Borbulevych", 
        "givenName": "O. Ya.", 
        "id": "sg:person.01242672206.13", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01242672206.13"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Institute for Single Crystals, National Academy of Sciences of the Ukraine, 60 prosp. Lenina, 310001, Kharkov, Ukraine", 
          "id": "http://www.grid.ac/institutes/grid.435063.7", 
          "name": [
            "Institute for Single Crystals, National Academy of Sciences of the Ukraine, 60 prosp. Lenina, 310001, Kharkov, Ukraine"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Shishkin", 
        "givenName": "O. V.", 
        "id": "sg:person.01023575604.49", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01023575604.49"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation", 
          "id": "http://www.grid.ac/institutes/grid.431939.5", 
          "name": [
            "A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Lyssenko", 
        "givenName": "K. A.", 
        "id": "sg:person.0704205214.44", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.0704205214.44"
        ], 
        "type": "Person"
      }, 
      {
        "affiliation": {
          "alternateName": "Department of Chemistry, Rostov State University, 7 ul. Zorge, 344090, Rostov-on-Don, Russian Federation", 
          "id": "http://www.grid.ac/institutes/grid.182798.d", 
          "name": [
            "Department of Chemistry, Rostov State University, 7 ul. Zorge, 344090, Rostov-on-Don, Russian Federation"
          ], 
          "type": "Organization"
        }, 
        "familyName": "Olekhnovich", 
        "givenName": "L. P.", 
        "id": "sg:person.015305011323.65", 
        "sameAs": [
          "https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.015305011323.65"
        ], 
        "type": "Person"
      }
    ], 
    "datePublished": "1999-01", 
    "datePublishedReg": "1999-01-01", 
    "description": "Oxidation of 4,6-di-tert-butylpyrogallol gave two dimeric products instead of the expected 4,6-di-tert-butyl-3-hydroxy-1,2-benzoquinone (2). It was established by X-ray diffraction analysis that the first product has the structure of tetra-tert-butyl-6, 10a-dihydroxy-1,2-dioxo-3,4a,7,9-1,2,4a, 10a-tetrahydrodibenzo-1,4-dioxine. From this it follows that compound 2 undergoes regio- and stereospecific dimerization according to the [2\u03c0+4\u03c0]-cycloaddition mechanism,viz, the hetero Diels\u2014Alder reaction. The double intensities of the signals in the1H NMR spectrum are indicative of a symmetrical structure of the second product, 2,6,4\u2032, 6\u2032-tetra-tert-butyl-4,4\u2032-dihyroxy-3,5,3\u2032,5\u2032-tetraoxo-4,4\u2032-bi(cyclohexene), which is a racemate of enantiomers formed upon recombination (r+r orl+l) of the intermediate of oxidation of pyrogallol, namely, of ther,l-stereogenic 3,5-di-tert-butyl-1-hydroxy-2,6-dioxocyclohex-3-enyl radical.", 
    "genre": "article", 
    "id": "sg:pub.10.1007/bf02494416", 
    "inLanguage": "en", 
    "isAccessibleForFree": false, 
    "isPartOf": [
      {
        "id": "sg:journal.1022309", 
        "issn": [
          "1063-5211", 
          "1026-3500"
        ], 
        "name": "Russian Chemical Bulletin", 
        "publisher": "Springer Nature", 
        "type": "Periodical"
      }, 
      {
        "issueNumber": "1", 
        "type": "PublicationIssue"
      }, 
      {
        "type": "PublicationVolume", 
        "volumeNumber": "48"
      }
    ], 
    "keywords": [
      "Diels-Alder reaction", 
      "intermediates of oxidation", 
      "hetero Diels-Alder reaction", 
      "tetra-tert", 
      "ray diffraction analysis", 
      "the1H NMR spectra", 
      "stereospecific dimerization", 
      "dimeric products", 
      "NMR spectra", 
      "oxidation products", 
      "diffraction analysis", 
      "second product", 
      "oxidation", 
      "double intensity", 
      "tert", 
      "symmetrical structure", 
      "first product", 
      "products", 
      "structure", 
      "stereogenic", 
      "regio", 
      "butyl-6", 
      "racemate", 
      "enantiomers", 
      "intermediates", 
      "reaction", 
      "pyrogallol", 
      "spectra", 
      "dimerization", 
      "viz", 
      "recombination", 
      "intensity", 
      "mechanism", 
      "analysis", 
      "signals", 
      "ther", 
      "tert-butylpyrogallol", 
      "compound 2 undergoes regio", 
      "undergoes regio", 
      "racemate of enantiomers"
    ], 
    "name": "Structures of oxidation products of 4,6-di-tert-butylpyrogallol", 
    "pagination": "139-146", 
    "productId": [
      {
        "name": "dimensions_id", 
        "type": "PropertyValue", 
        "value": [
          "pub.1035289330"
        ]
      }, 
      {
        "name": "doi", 
        "type": "PropertyValue", 
        "value": [
          "10.1007/bf02494416"
        ]
      }
    ], 
    "sameAs": [
      "https://doi.org/10.1007/bf02494416", 
      "https://app.dimensions.ai/details/publication/pub.1035289330"
    ], 
    "sdDataset": "articles", 
    "sdDatePublished": "2021-12-01T19:12", 
    "sdLicense": "https://scigraph.springernature.com/explorer/license/", 
    "sdPublisher": {
      "name": "Springer Nature - SN SciGraph project", 
      "type": "Organization"
    }, 
    "sdSource": "s3://com-springernature-scigraph/baseset/20211201/entities/gbq_results/article/article_329.jsonl", 
    "type": "ScholarlyArticle", 
    "url": "https://doi.org/10.1007/bf02494416"
  }
]
 

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/bf02494416'

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/bf02494416'

Turtle is a human-readable linked data format.

curl -H 'Accept: text/turtle' 'https://scigraph.springernature.com/pub.10.1007/bf02494416'

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

curl -H 'Accept: application/rdf+xml' 'https://scigraph.springernature.com/pub.10.1007/bf02494416'


 

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

137 TRIPLES      21 PREDICATES      65 URIs      58 LITERALS      6 BLANK NODES

Subject Predicate Object
1 sg:pub.10.1007/bf02494416 schema:about anzsrc-for:03
2 schema:author Na37a11e215ea4db6b25d5a493d7d35bf
3 schema:datePublished 1999-01
4 schema:datePublishedReg 1999-01-01
5 schema:description Oxidation of 4,6-di-tert-butylpyrogallol gave two dimeric products instead of the expected 4,6-di-tert-butyl-3-hydroxy-1,2-benzoquinone (2). It was established by X-ray diffraction analysis that the first product has the structure of tetra-tert-butyl-6, 10a-dihydroxy-1,2-dioxo-3,4a,7,9-1,2,4a, 10a-tetrahydrodibenzo-1,4-dioxine. From this it follows that compound 2 undergoes regio- and stereospecific dimerization according to the [2π+4π]-cycloaddition mechanism,viz, the hetero Diels—Alder reaction. The double intensities of the signals in the1H NMR spectrum are indicative of a symmetrical structure of the second product, 2,6,4′, 6′-tetra-tert-butyl-4,4′-dihyroxy-3,5,3′,5′-tetraoxo-4,4′-bi(cyclohexene), which is a racemate of enantiomers formed upon recombination (r+r orl+l) of the intermediate of oxidation of pyrogallol, namely, of ther,l-stereogenic 3,5-di-tert-butyl-1-hydroxy-2,6-dioxocyclohex-3-enyl radical.
6 schema:genre article
7 schema:inLanguage en
8 schema:isAccessibleForFree false
9 schema:isPartOf N1658e2492b804bf280c7bbb1ce951de3
10 N38c96d3535f54efe9b7804f731f8838e
11 sg:journal.1022309
12 schema:keywords Diels-Alder reaction
13 NMR spectra
14 analysis
15 butyl-6
16 compound 2 undergoes regio
17 diffraction analysis
18 dimeric products
19 dimerization
20 double intensity
21 enantiomers
22 first product
23 hetero Diels-Alder reaction
24 intensity
25 intermediates
26 intermediates of oxidation
27 mechanism
28 oxidation
29 oxidation products
30 products
31 pyrogallol
32 racemate
33 racemate of enantiomers
34 ray diffraction analysis
35 reaction
36 recombination
37 regio
38 second product
39 signals
40 spectra
41 stereogenic
42 stereospecific dimerization
43 structure
44 symmetrical structure
45 tert
46 tert-butylpyrogallol
47 tetra-tert
48 the1H NMR spectra
49 ther
50 undergoes regio
51 viz
52 schema:name Structures of oxidation products of 4,6-di-tert-butylpyrogallol
53 schema:pagination 139-146
54 schema:productId N2a5c395aab7a42e7ba380257c3600d37
55 Nc1d58d0d60114406a9013c7b3538a5a5
56 schema:sameAs https://app.dimensions.ai/details/publication/pub.1035289330
57 https://doi.org/10.1007/bf02494416
58 schema:sdDatePublished 2021-12-01T19:12
59 schema:sdLicense https://scigraph.springernature.com/explorer/license/
60 schema:sdPublisher N50150ff3950c4cc7be850039141c2dff
61 schema:url https://doi.org/10.1007/bf02494416
62 sgo:license sg:explorer/license/
63 sgo:sdDataset articles
64 rdf:type schema:ScholarlyArticle
65 N1658e2492b804bf280c7bbb1ce951de3 schema:volumeNumber 48
66 rdf:type schema:PublicationVolume
67 N2a5c395aab7a42e7ba380257c3600d37 schema:name dimensions_id
68 schema:value pub.1035289330
69 rdf:type schema:PropertyValue
70 N2d0893c560e64426a5f368cedbf23169 rdf:first sg:person.010113170153.15
71 rdf:rest Nff8c1c5ee2b448bdbaa4da1af2f6e48c
72 N38c96d3535f54efe9b7804f731f8838e schema:issueNumber 1
73 rdf:type schema:PublicationIssue
74 N3cc236ebc1d34976aa2b8691f177dbdd rdf:first sg:person.01023575604.49
75 rdf:rest Nf14d5e78f03f48d8a74d697fbb93339b
76 N50150ff3950c4cc7be850039141c2dff schema:name Springer Nature - SN SciGraph project
77 rdf:type schema:Organization
78 Na37a11e215ea4db6b25d5a493d7d35bf rdf:first sg:person.014520050323.79
79 rdf:rest N2d0893c560e64426a5f368cedbf23169
80 Nc1d58d0d60114406a9013c7b3538a5a5 schema:name doi
81 schema:value 10.1007/bf02494416
82 rdf:type schema:PropertyValue
83 Ne533bf348e134335b838c53430e25da0 rdf:first sg:person.015305011323.65
84 rdf:rest rdf:nil
85 Nf14d5e78f03f48d8a74d697fbb93339b rdf:first sg:person.0704205214.44
86 rdf:rest Ne533bf348e134335b838c53430e25da0
87 Nff8c1c5ee2b448bdbaa4da1af2f6e48c rdf:first sg:person.01242672206.13
88 rdf:rest N3cc236ebc1d34976aa2b8691f177dbdd
89 anzsrc-for:03 schema:inDefinedTermSet anzsrc-for:
90 schema:name Chemical Sciences
91 rdf:type schema:DefinedTerm
92 sg:journal.1022309 schema:issn 1026-3500
93 1063-5211
94 schema:name Russian Chemical Bulletin
95 schema:publisher Springer Nature
96 rdf:type schema:Periodical
97 sg:person.010113170153.15 schema:affiliation grid-institutes:grid.182798.d
98 schema:familyName Lyubchenko
99 schema:givenName S. N.
100 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.010113170153.15
101 rdf:type schema:Person
102 sg:person.01023575604.49 schema:affiliation grid-institutes:grid.435063.7
103 schema:familyName Shishkin
104 schema:givenName O. V.
105 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01023575604.49
106 rdf:type schema:Person
107 sg:person.01242672206.13 schema:affiliation grid-institutes:grid.431939.5
108 schema:familyName Borbulevych
109 schema:givenName O. Ya.
110 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.01242672206.13
111 rdf:type schema:Person
112 sg:person.014520050323.79 schema:affiliation grid-institutes:grid.182798.d
113 schema:familyName Shif
114 schema:givenName A. I.
115 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.014520050323.79
116 rdf:type schema:Person
117 sg:person.015305011323.65 schema:affiliation grid-institutes:grid.182798.d
118 schema:familyName Olekhnovich
119 schema:givenName L. P.
120 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.015305011323.65
121 rdf:type schema:Person
122 sg:person.0704205214.44 schema:affiliation grid-institutes:grid.431939.5
123 schema:familyName Lyssenko
124 schema:givenName K. A.
125 schema:sameAs https://app.dimensions.ai/discover/publication?and_facet_researcher=ur.0704205214.44
126 rdf:type schema:Person
127 grid-institutes:grid.182798.d schema:alternateName Department of Chemistry, Rostov State University, 7 ul. Zorge, 344090, Rostov-on-Don, Russian Federation
128 Scientific Research Institute of Physical and Organic Chemistry at Rostov State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation
129 schema:name Department of Chemistry, Rostov State University, 7 ul. Zorge, 344090, Rostov-on-Don, Russian Federation
130 Scientific Research Institute of Physical and Organic Chemistry at Rostov State University, 194/2 prosp. Stachki, 344090, Rostov-on-Don, Russian Federation
131 rdf:type schema:Organization
132 grid-institutes:grid.431939.5 schema:alternateName A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation
133 schema:name A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation
134 rdf:type schema:Organization
135 grid-institutes:grid.435063.7 schema:alternateName Institute for Single Crystals, National Academy of Sciences of the Ukraine, 60 prosp. Lenina, 310001, Kharkov, Ukraine
136 schema:name Institute for Single Crystals, National Academy of Sciences of the Ukraine, 60 prosp. Lenina, 310001, Kharkov, Ukraine
137 rdf:type schema:Organization
 




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


...