DOI: 10.1002/adsc.200303218. Is it Possible to Achieve Highly Selective Oxidations in Supercritical Water? Aerobic Oxidation of Methylaromatic Compounds

Is it Possible to Achieve Highly Selective Oxidations in Supercritical Water? Aerobic Oxidation of Methylaromatic Compounds

10.1002/adsc.200303218

Crossref journal-article

Wiley

Advanced Synthesis & Catalysis (311)

Abstract

AbstractWe have demonstrated that different methylaromatic compounds [1,4‐dimethylbenzene (p‐xylene), 1,3‐dimethylbenzene (m‐xylene), 1,2‐dimethylbenzene (o‐xylene), 1,3,5‐trimethylbenzene (mesitylene) and 1,2,4‐trimethylbenzene (pseudocumene)] can be aerobically oxidized in supercritical water (scH2O) using manganese(II) bromide as catalyst to give corresponding carboxylic acids in the continuous mode over a sustained period of time in good yield. No partially oxidized intermediates (i.e., toluic acid and benzaldehydes) were detected for the dimethylbenzenes and mesitylene reactions. By fine tuning pressure and temperature, scH2O becomes a solvent with physical properties suitable for single‐phase oxidation since both organic substrate and oxygen are soluble in scH2O. There is a strong structural similarity of metal/bromide coordination compounds in the active oxidation solvents (acetic acid and scH2O) which does not exist in the much less active H2O at lower temperatures. This may account for the successful catalysis of the reactions reported herein. Aromatic acids produced by the loss of one methyl group occurred in all of these reactions, i.e., 3–6% benzoic acid formed during the oxidation of the dimethylbenzenes. Part of this loss is thought to be due to thermal decarboxylation. The thermal decarboxylation process is monitored via Raman spectroscopy.

Bibliography

GarciaâVerdugo, E., Venardou, E., Thomas, W. B., Whiston, K., Partenheimer, W., Hamley, P. A., & Poliakoff, M. (2004). Is it Possible to Achieve Highly Selective Oxidations in Supercritical Water? Aerobic Oxidation of Methylaromatic Compounds. Advanced Synthesis & Catalysis, 346(2â3), 307â316. Portico.

Authors 7

Eduardo Garcia‐Verdugo (first)
Eleni Venardou (additional)
W. Barry Thomas (additional)
Keith Whiston (additional)
Walter Partenheimer (additional)
Paul A. Hamley (additional)
Martyn Poliakoff (additional)

References 53 Referenced 43

10.1016/0920-5861(94)00138-R
10.1039/b303160h
{'key': 'e_1_2_1_3_2', 'first-page': '31', 'volume': '32', 'author': 'Zakharov I. V.', 'year': '1991', 'journal-title': 'Kinet. i Katali'} / Kinet. i Katali by Zakharov I. V. (1991)
10.1021/i300003a011
10.1006/jcat.1993.1176
{'key': 'e_1_2_1_6_2', 'first-page': '357', 'volume': '20', 'author': 'Aleksandrov V. N.', 'year': '1979', 'journal-title': 'Kinetika i Kataliz'} / Kinetika i Kataliz by Aleksandrov V. N. (1979)
10.1246/bcsj.49.1632
N. R.Nowicki J. D.Lowry US Patent 4 892 970 1990.
10.1021/cr000668w
10.1063/1.555632
{'key': 'e_1_2_1_11_2', 'volume-title': 'CRC Handbook of Chemistry and Physics: a ready reference book of chemical and physical data', 'author': 'Weast R. C.', 'year': '1972'} / CRC Handbook of Chemistry and Physics: a ready reference book of chemical and physical data by Weast R. C. (1972)
10.1063/1.555643
10.1021/ie980204c
10.1039/a906401j
10.1021/ja9925251
10.1021/ie000964z
10.1002/1521-3773(20020215)41:4<623::AID-ANIE623>3.0.CO;2-1
10.1039/b212394k
10.1002/(SICI)1521-4125(199911)22:11<903::AID-CEAT903>3.0.CO;2-E
10.1039/b202087b
10.1039/b305409h
{'key': 'e_1_2_1_22_2', 'volume-title': 'An Introduction to Industrial Organic Chemistry', 'author': 'Wiseman P.', 'year': '1979'} / An Introduction to Industrial Organic Chemistry by Wiseman P. (1979)
10.1002/9783527616688
W. Partenheimer J. A. Kaduk Deactivation Mechanisms in Liquid Phase Oxidation Caused by Carboxylic Acids In:Proceedings from the 4th International Symposium on Activation of Dioxygen and Homogeneous Catalytic Oxidation 613–621 Elsevier New York. (10.1016/S0167-2991(08)62881-5)
10.1016/S1381-1169(03)00407-2
10.1002/1615-4169(200206)344:3/4<385::AID-ADSC385>3.0.CO;2-G
10.1016/S0896-8446(98)00084-9
10.1021/ie010952t
N. R.Nowicki J. D.Lowry US Patent 4 892 970 1990.
{'key': 'e_1_2_1_30_2', 'volume-title': 'A Method for the Preparation of Pyromellitic Acid from Durene via Liquid Phase Oxidation.', 'author': 'Partenheimer W.', 'year': '1994'} / A Method for the Preparation of Pyromellitic Acid from Durene via Liquid Phase Oxidation. by Partenheimer W. (1994)
10.1021/ja01021a023
10.1021/ja00711a041
{'key': 'e_1_2_1_33_2', 'volume-title': 'Metal Catalyzed Oxidations of Organic Compounds', 'author': 'Sheldon R. A.', 'year': '1981'} / Metal Catalyzed Oxidations of Organic Compounds by Sheldon R. A. (1981)
10.1016/S0896-8446(02)00241-3
10.1366/000370203769699207
10.1016/S1381-1169(01)00169-8
10.1021/ic990653k
10.1021/ic991213w
10.1002/1615-4169(20010129)343:1<102::AID-ADSC102>3.0.CO;2-Q
10.1016/S1381-1169(03)00407-2
10.1016/S1381-1169(03)00421-7
10.1021/ie0107789
10.1039/c39790000536
10.1021/jp990435c
{'key': 'e_1_2_1_45_2', 'volume-title': 'Metals Ions in Solution', 'author': 'Burgess J.', 'year': '1978'} / Metals Ions in Solution by Burgess J. (1978)
10.1016/0022-1902(77)80026-2
10.1039/dt9830001565
{'key': 'e_1_2_1_48_2', 'first-page': '2145', 'volume-title': 'The Chemistry of Nonaqueous Solvents III', 'author': 'Popov A. I.', 'year': '1970'} / The Chemistry of Nonaqueous Solvents III by Popov A. I. (1970)
10.1016/S0149-1970(00)00080-9
10.1021/cr970036i
10.1021/ie010473u
10.1002/adsc.200303187
Observations from the laboratory of W. Partenheimer.

Dates

Type	When
Created	21 years, 4 months ago (March 29, 2004, 10:03 a.m.)
Deposited	1 year, 11 months ago (Aug. 31, 2023, 9:16 a.m.)
Indexed	1 year, 10 months ago (Oct. 17, 2023, 12:58 a.m.)
Issued	21 years, 6 months ago (Feb. 1, 2004)
Published	21 years, 6 months ago (Feb. 1, 2004)
Published Online	21 years, 4 months ago (March 29, 2004)
Published Print	21 years, 6 months ago (Feb. 1, 2004)

Funders 0

None

BibTeX

@article{Garcia_Verdugo_2004, title={Is it Possible to Achieve Highly Selective Oxidations in Supercritical Water? Aerobic Oxidation of Methylaromatic Compounds}, volume={346}, ISSN={1615-4169}, url={http://dx.doi.org/10.1002/adsc.200303218}, DOI={10.1002/adsc.200303218}, number={2–3}, journal={Advanced Synthesis & Catalysis}, publisher={Wiley}, author={Garcia‐Verdugo, Eduardo and Venardou, Eleni and Thomas, W. Barry and Whiston, Keith and Partenheimer, Walter and Hamley, Paul A. and Poliakoff, Martyn}, year={2004}, month=feb, pages={307–316} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2023,
        10,
        17
      ]
    ],
    "date-time": "2023-10-17T04:58:07Z",
    "timestamp": 1697518687337
  },
  "reference-count": 53,
  "publisher": "Wiley",
  "issue": "2-3",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            2004,
            3,
            29
          ]
        ],
        "date-time": "2004-03-29T00:00:00Z",
        "timestamp": 1080518400000
      },
      "content-version": "vor",
      "delay-in-days": 57,
      "URL": "http://onlinelibrary.wiley.com/termsAndConditions#vor"
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        2004,
        2
      ]
    ]
  },
  "abstract": "<jats:title>Abstract</jats:title><jats:p>We have demonstrated that different methylaromatic compounds [1,4\u2010dimethylbenzene (<jats:italic>p</jats:italic>\u2010xylene), 1,3\u2010dimethylbenzene (<jats:italic>m</jats:italic>\u2010xylene), 1,2\u2010dimethylbenzene (<jats:italic>o</jats:italic>\u2010xylene), 1,3,5\u2010trimethylbenzene (mesitylene) and 1,2,4\u2010trimethylbenzene (pseudocumene)] can be aerobically oxidized in supercritical water (scH<jats:sub>2</jats:sub>O) using manganese(II) bromide as catalyst to give corresponding carboxylic acids in the continuous mode over a sustained period of time in good yield. No partially oxidized intermediates (i.e., toluic acid and benzaldehydes) were detected for the dimethylbenzenes and mesitylene reactions. By fine tuning pressure and temperature, scH<jats:sub>2</jats:sub>O becomes a solvent with physical properties suitable for single\u2010phase oxidation since both organic substrate and oxygen are soluble in scH<jats:sub>2</jats:sub>O. There is a strong structural similarity of metal/bromide coordination compounds in the active oxidation solvents (acetic acid and scH<jats:sub>2</jats:sub>O) which does not exist in the much less active H<jats:sub>2</jats:sub>O at lower temperatures. This may account for the successful catalysis of the reactions reported herein. Aromatic acids produced by the loss of one methyl group occurred in all of these reactions, i.e., 3\u20136% benzoic acid formed during the oxidation of the dimethylbenzenes. Part of this loss is thought to be due to thermal decarboxylation. The thermal decarboxylation process is monitored <jats:italic>via</jats:italic> Raman spectroscopy.</jats:p>",
  "DOI": "10.1002/adsc.200303218",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2004,
        3,
        29
      ]
    ],
    "date-time": "2004-03-29T15:03:52Z",
    "timestamp": 1080572632000
  },
  "page": "307-316",
  "source": "Crossref",
  "is-referenced-by-count": 43,
  "title": "Is it Possible to Achieve Highly Selective Oxidations in Supercritical Water? Aerobic Oxidation of Methylaromatic Compounds",
  "prefix": "10.1002",
  "volume": "346",
  "author": [
    {
      "given": "Eduardo",
      "family": "Garcia\u2010Verdugo",
      "sequence": "first",
      "affiliation": []
    },
    {
      "given": "Eleni",
      "family": "Venardou",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "W.\u2005Barry",
      "family": "Thomas",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Keith",
      "family": "Whiston",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Walter",
      "family": "Partenheimer",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Paul\u2005A.",
      "family": "Hamley",
      "sequence": "additional",
      "affiliation": []
    },
    {
      "given": "Martyn",
      "family": "Poliakoff",
      "sequence": "additional",
      "affiliation": []
    }
  ],
  "member": "311",
  "published-online": {
    "date-parts": [
      [
        2004,
        3,
        29
      ]
    ]
  },
  "reference": [
    {
      "key": "e_1_2_1_1_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0920-5861(94)00138-R"
    },
    {
      "key": "e_1_2_1_2_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b303160h"
    },
    {
      "key": "e_1_2_1_3_2",
      "first-page": "31",
      "volume": "32",
      "author": "Zakharov I. V.",
      "year": "1991",
      "journal-title": "Kinet. i Katali"
    },
    {
      "key": "e_1_2_1_4_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/i300003a011"
    },
    {
      "key": "e_1_2_1_5_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1006/jcat.1993.1176"
    },
    {
      "key": "e_1_2_1_6_2",
      "first-page": "357",
      "volume": "20",
      "author": "Aleksandrov V. N.",
      "year": "1979",
      "journal-title": "Kinetika i Kataliz"
    },
    {
      "key": "e_1_2_1_7_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1246/bcsj.49.1632"
    },
    {
      "key": "e_1_2_1_8_2",
      "unstructured": "N.\u2005R.Nowicki J.\u2005D.Lowry US Patent 4 892 970 1990."
    },
    {
      "key": "e_1_2_1_9_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr000668w"
    },
    {
      "key": "e_1_2_1_10_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.555632"
    },
    {
      "key": "e_1_2_1_11_2",
      "volume-title": "CRC Handbook of Chemistry and Physics: a ready reference book of chemical and physical data",
      "author": "Weast R. C.",
      "year": "1972"
    },
    {
      "key": "e_1_2_1_12_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1063/1.555643"
    },
    {
      "key": "e_1_2_1_13_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ie980204c"
    },
    {
      "key": "e_1_2_1_14_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/a906401j"
    },
    {
      "key": "e_1_2_1_15_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja9925251"
    },
    {
      "key": "e_1_2_1_16_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ie000964z"
    },
    {
      "key": "e_1_2_1_17_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/1521-3773(20020215)41:4<623::AID-ANIE623>3.0.CO;2-1"
    },
    {
      "key": "e_1_2_1_18_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b212394k"
    },
    {
      "key": "e_1_2_1_19_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/(SICI)1521-4125(199911)22:11<903::AID-CEAT903>3.0.CO;2-E"
    },
    {
      "key": "e_1_2_1_20_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b202087b"
    },
    {
      "key": "e_1_2_1_21_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/b305409h"
    },
    {
      "key": "e_1_2_1_22_2",
      "volume-title": "An Introduction to Industrial Organic Chemistry",
      "author": "Wiseman P.",
      "year": "1979"
    },
    {
      "key": "e_1_2_1_23_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/9783527616688"
    },
    {
      "key": "e_1_2_1_24_2",
      "doi-asserted-by": "crossref",
      "unstructured": "W. Partenheimer J.\u2005A. Kaduk Deactivation Mechanisms in Liquid Phase Oxidation Caused by Carboxylic Acids In:Proceedings from the 4th International Symposium on Activation of Dioxygen and Homogeneous Catalytic Oxidation 613\u2013621 Elsevier New York.",
      "DOI": "10.1016/S0167-2991(08)62881-5"
    },
    {
      "key": "e_1_2_1_25_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S1381-1169(03)00407-2"
    },
    {
      "key": "e_1_2_1_26_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/1615-4169(200206)344:3/4<385::AID-ADSC385>3.0.CO;2-G"
    },
    {
      "key": "e_1_2_1_27_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S0896-8446(98)00084-9"
    },
    {
      "key": "e_1_2_1_28_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ie010952t"
    },
    {
      "key": "e_1_2_1_29_2",
      "unstructured": "N.\u2005R.Nowicki J.\u2005D.Lowry US Patent 4 892 970 1990."
    },
    {
      "key": "e_1_2_1_30_2",
      "volume-title": "A Method for the Preparation of Pyromellitic Acid from Durene via Liquid Phase Oxidation.",
      "author": "Partenheimer W.",
      "year": "1994"
    },
    {
      "key": "e_1_2_1_31_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja01021a023"
    },
    {
      "key": "e_1_2_1_32_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ja00711a041"
    },
    {
      "key": "e_1_2_1_33_2",
      "volume-title": "Metal Catalyzed Oxidations of Organic Compounds",
      "author": "Sheldon R. A.",
      "year": "1981"
    },
    {
      "key": "e_1_2_1_34_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S0896-8446(02)00241-3"
    },
    {
      "key": "e_1_2_1_35_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1366/000370203769699207"
    },
    {
      "key": "e_1_2_1_36_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S1381-1169(01)00169-8"
    },
    {
      "key": "e_1_2_1_37_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic990653k"
    },
    {
      "key": "e_1_2_1_38_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ic991213w"
    },
    {
      "key": "e_1_2_1_39_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/1615-4169(20010129)343:1<102::AID-ADSC102>3.0.CO;2-Q"
    },
    {
      "key": "e_1_2_1_40_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S1381-1169(03)00407-2"
    },
    {
      "key": "e_1_2_1_41_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S1381-1169(03)00421-7"
    },
    {
      "key": "e_1_2_1_42_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ie0107789"
    },
    {
      "key": "e_1_2_1_43_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/c39790000536"
    },
    {
      "key": "e_1_2_1_44_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/jp990435c"
    },
    {
      "key": "e_1_2_1_45_2",
      "volume-title": "Metals Ions in Solution",
      "author": "Burgess J.",
      "year": "1978"
    },
    {
      "key": "e_1_2_1_46_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/0022-1902(77)80026-2"
    },
    {
      "key": "e_1_2_1_47_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/dt9830001565"
    },
    {
      "key": "e_1_2_1_48_2",
      "first-page": "2145",
      "volume-title": "The Chemistry of Nonaqueous Solvents III",
      "author": "Popov A. I.",
      "year": "1970"
    },
    {
      "key": "e_1_2_1_49_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1016/S0149-1970(00)00080-9"
    },
    {
      "key": "e_1_2_1_50_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr970036i"
    },
    {
      "key": "e_1_2_1_51_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/ie010473u"
    },
    {
      "key": "e_1_2_1_52_2",
      "doi-asserted-by": "publisher",
      "DOI": "10.1002/adsc.200303187"
    },
    {
      "key": "e_1_2_1_53_2",
      "unstructured": "Observations from the laboratory of W. Partenheimer."
    }
  ],
  "container-title": "Advanced Synthesis &amp; Catalysis",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://api.wiley.com/onlinelibrary/tdm/v1/articles/10.1002%2Fadsc.200303218",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://onlinelibrary.wiley.com/doi/pdf/10.1002/adsc.200303218",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2023,
        8,
        31
      ]
    ],
    "date-time": "2023-08-31T13:16:38Z",
    "timestamp": 1693487798000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://onlinelibrary.wiley.com/doi/10.1002/adsc.200303218"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        2004,
        2
      ]
    ]
  },
  "references-count": 53,
  "journal-issue": {
    "issue": "2-3",
    "published-print": {
      "date-parts": [
        [
          2004,
          2
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1002/adsc.200303218"
  ],
  "URL": "http://dx.doi.org/10.1002/adsc.200303218",
  "relation": {},
  "ISSN": [
    "1615-4150",
    "1615-4169"
  ],
  "subject": [],
  "container-title-short": "Adv Synth Catal",
  "published": {
    "date-parts": [
      [
        2004,
        2
      ]
    ]
  }
}