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EP1021412A1 - Nitration of aromatic compounds - Google Patents

Nitration of aromatic compounds

Info

Publication number
EP1021412A1
EP1021412A1 EP96941744A EP96941744A EP1021412A1 EP 1021412 A1 EP1021412 A1 EP 1021412A1 EP 96941744 A EP96941744 A EP 96941744A EP 96941744 A EP96941744 A EP 96941744A EP 1021412 A1 EP1021412 A1 EP 1021412A1
Authority
EP
European Patent Office
Prior art keywords
process according
sulphilimine
diaryl
alkylaryisulphilimine
electron
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP96941744A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ross Wood Millar
Robert Peter Claridge
John Paul Benet Sandall
Claire Thompson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qinetiq Ltd
Original Assignee
UK Secretary of State for Defence
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UK Secretary of State for Defence filed Critical UK Secretary of State for Defence
Publication of EP1021412A1 publication Critical patent/EP1021412A1/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/72—Nitrogen atoms
    • C07D213/76—Nitrogen atoms to which a second hetero atom is attached
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/10—Preparation of nitro compounds by substitution of functional groups by nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
    • C07C201/06—Preparation of nitro compounds
    • C07C201/16—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C07C381/10—Compounds containing sulfur atoms doubly-bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/61—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/42—One nitrogen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/16—Halogen atoms; Nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/20—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/44—One nitrogen atom with halogen atoms attached to the two other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
    • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
    • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
    • C07D251/40—Nitrogen atoms
    • C07D251/42—One nitrogen atom
    • C07D251/46—One nitrogen atom with oxygen or sulfur atoms attached to the two other ring carbon atoms

Definitions

  • the present invention relates to a process for the nitration of aromatic compounds and in particular the nitration of both heterocyclic and carbocyclic electron deficient aromatics
  • Typical heterocyclic electron deficient aromatics are such substances as pyridines, diazines (especially pyrimidines and pyrazines) and triazines whilst the carbocyclic electron deficient aromatics may be described as being benzenoid aromatics substituted with electron-withdrawing groups.
  • an electron-deficient aromatic is defined as either a heterocyclic or carbocyclic aromatic bearing a leaving group which is commonly displaced by nitrogen nucleophiles.
  • Such leaving groups include halogens, nitro groups, alkoxy groups and nitrile groups
  • nitroheterocycles may be prepared by oxidation of dialkylsulphilimine and related phosphinimine intermediates derived from aminoheterocycles (Taylor et al, J Org Chem 47 552 (1982) and Rakitin et al, Khim Geterot. Soed. 1536 (1990), and Coburn et al J Het. Chem 23 421 ( 1986) and J Het Chem.
  • a method of preparing N-aryi- and N-heteroarylsulphilimine derivatives of electron-deficient carbocyclic and heterocyclic aromatics which comprises the steps of
  • S,S-d ⁇ phenylsulph ⁇ l ⁇ m ⁇ ne is particularly preferred since this is a commercially available mate ⁇ al
  • Other possible sulphilimmes include S- methyl-S-phenyl- and S,S-d ⁇ methylsulph ⁇ l ⁇ m ⁇ ne
  • the polar solvent is an alcohol or an ether, most preferably an alcohol of low molecular weight such as ethanol or other lower alcohols with chain length 4 carbon atoms or less
  • the ether may be a cyclic ether such as tetrahydrofuran (THF) or 1 ,4-d ⁇ oxane
  • THF tetrahydrofuran
  • 1 ,4-d ⁇ oxane a substantially more economical use of the sulphilimine reagent is achieved
  • the method of Vlasova et al involves use of three equivalents of S,S-diphenylsulphilimine to one equivalent of aromatic reagent
  • the present process only two equivalents are used of which one is recovered in the form of a salt (eg. the halide salt) and may be reconverted to the diphenylsuiphilimine
  • R l and R are independently alkyl and/or aryl groups and M is lithium, sodium or potassium.
  • a particularly preferred class of reagents of this type are the N-lithio salts and especially N-lithio-S,S-diphenylsulphilimine.
  • novel reagents may be readily prepared by reacting the corresponding sulphilimine with alkyl lithiums with chain length 1 to 4 atoms, preferably n- butyllithium, alkali metal hydrides such as lithium, sodium or potassium hydrides, alkali metal hydrogenous bases such as lithium, sodium or potassium N,N- di(isopropyl)amides or the respective N,N-bis(trimethylsilyl)amides or other suitable base.
  • alkyl lithiums with chain length 1 to 4 atoms, preferably n- butyllithium
  • alkali metal hydrides such as lithium, sodium or potassium hydrides
  • alkali metal hydrogenous bases such as lithium, sodium or potassium N,N- di(isopropyl)amides or the respective N,N-bis(trimethylsilyl)amides or other suitable base.
  • the N-alkali metal salt used is an N-lithio sulphilimine salt and particularly preferred is N-lithio-S,S-diphenylsulphilimine which is readily derived from the commercially available compound S,S-diphenylsu!philimine.
  • N-lithio-S,S-diphenylsulphilimine which is readily derived from the commercially available compound S,S-diphenylsu!philimine.
  • the corresponding salts derived from sodium and potassium would react in a similar manner these are likely to be more difficult to prepare than the lithium salts and therefore comprise less desirable reagents from a practical point of view
  • aprotic solvent 1 dimethoxyethane, diethyleneglycol dimethylether (diglyme) or most especially tetrahydrofuran are preferred.
  • the present invention provides a process for the nitration of electron-deficient carbocyclic and heterocyclic aromatic compounds which comprises the steps of-
  • step (b) treating the product of step (a) with an oxidising agent to convert the sulphilimino group to a nitro-group;
  • step (b) isolating the nitrated aromatic compound obtained in step (b).
  • the reaction of step (a) is as previously described
  • the inventors have found, in contradistinction to earlier work with phosphinimines, that the sulphilimine derivatives may be readily oxidised with commercially available oxidants such as m-chloroperbenzoic acid
  • any peroxycarboxvlic acid may be employed such as va ⁇ ous perbenzoic acids, particularly m-chloroperbenzoic acid, peracetic acid or peroxyt ⁇ fluoroacetic acid
  • Yields in the first, nucleophilic substitution, step are typically in the range of 60% to quantitative and in the second, oxidation, step in the range of 10 to 63% In general, even in the case of compounds which have previously been obtainable via conventional electrophilic nitrations, the yields are greater with the present two-step process than have been achieved before
  • Example 1 Prepnrntioii or 2-cl ⁇ loro-6- ⁇ itropyrnzine (XXI) from 2.6- dichloropyrnzine (XXXI).
  • 1st step S,S-diphenylsulphilimine ( 1 08g, 4 92 mmol, 2 equiv ) was weighed into a 100ml triple-necked round-bottomed flask THF ( 15 ml) was added, causing the solid sulphilimine to dissolve Pentachloropyridine (XXXV, 0 618g, 2 46 mmol, 1 equiv ) was added to the solution m the flask The central neck of the flask was fitted with a water condenser, and the remaining two necks fitted with glass stoppers A magnetic stirrer was used to stir the solution The contents of the flask was stirred and refluxed for 4 hr, using a paraffin oil bath heated on a hotplate stirrer device At the end of the 4 hr the reaction mixture was cooled to room temperature and the white precipitate of diphenylaminosulphonium chloride which had appeared during the reaction was removed by filtration This salt was saved for recycling
  • the oxidising agent 3-chloroperoxybenzoic acid (0 497g, 2 87 mmol, 6 equiv ) was weighed out into a 100ml triple-necked round-bottomed flask The three necks of the flask were fitted with a stopper, a water condenser and a thermometer, and a magnetic stirrer bar was placed in the flask HPLC grade 1 ,2-dichloroethane (20 ml) was added to the flask and the contents of the flask were cooled to -5°C by suspending the flask in a plastic bowl filled with a mixture of ice and salt (i e.
  • 1st step S,S-diphenylsulphilim ⁇ ne ( 1 08g, 4 92 mmol) was weighed into a 100ml triple-necked round-bottomed flask THF (20 ml) was added, causing the solid sulphilimine to dissolve.
  • 2,4-dinitrophenyl- S,S-diphenylsulphilimine was prepared by the method of Tamura et al (J Org Chem 38, 4324 ( 1973))
  • Example 10 Preparation of 1.2.4-trinitrohenzene (XXIIIB) from l-flnoro-3.4- dinitrobenzene (XXXVIII).
  • Example 12 Preparation of 2-nitro-3.5.6-trifl ⁇ oropyridine (XXX) from 2.3.5.6- tetraflnoropyridine (XXXVII).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pyridine Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP96941744A 1995-12-16 1996-12-09 Nitration of aromatic compounds Withdrawn EP1021412A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB9525789A GB2308119A (en) 1995-12-16 1995-12-16 Nitration of aromatic compounds sulphilimines
GB9525789 1995-12-16
PCT/GB1996/003020 WO1997022590A1 (en) 1995-12-16 1996-12-09 Nitration of aromatic compounds

Publications (1)

Publication Number Publication Date
EP1021412A1 true EP1021412A1 (en) 2000-07-26

Family

ID=10785573

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96941744A Withdrawn EP1021412A1 (en) 1995-12-16 1996-12-09 Nitration of aromatic compounds

Country Status (8)

Country Link
EP (1) EP1021412A1 (no)
CA (1) CA2240644A1 (no)
CZ (1) CZ291529B6 (no)
GB (2) GB2308119A (no)
IL (1) IL124960A (no)
NO (1) NO309524B1 (no)
WO (1) WO1997022590A1 (no)
ZA (1) ZA9610559B (no)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2491225B (en) * 2010-03-16 2013-05-01 Qinetiq Ltd MEMS detonator
CN110330432B (zh) * 2019-07-29 2022-07-29 重庆医药高等专科学校 一种芳香硝基化合物的合成方法
CN118063408B (zh) * 2024-02-21 2024-11-19 北京农学院 一种4-环烷基苯并-1-氧杂磺酰亚胺类化合物的制备方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMISTRY & TECHNOLOGY OF EXPLOSIVES, vol. 1, 1964, PERGAMON PRESS, pages 326 *
See also references of WO9722590A1 *
TAMURA Y. ET AL: "Reactions of N-unsubstituted arylsulphilimines with acylating agents and with activated halobenzenes, alkynes and alkenes.", JOURNAL OF ORGANIC CHEMISTRY, vol. 38, no. 25, 1973, EASTON, US, pages 4324 - 4328 *

Also Published As

Publication number Publication date
GB2322857B (en) 2000-03-29
NO982753L (no) 1998-08-17
GB2308119A (en) 1997-06-18
WO1997022590A1 (en) 1997-06-26
ZA9610559B (en) 1997-06-24
GB9811567D0 (en) 1998-07-29
GB2322857A (en) 1998-09-09
GB9525789D0 (en) 1996-02-14
NO309524B1 (no) 2001-02-12
IL124960A (en) 2003-02-12
CZ186798A3 (cs) 1998-10-14
IL124960A0 (en) 1999-01-26
CZ291529B6 (cs) 2003-03-12
NO982753D0 (no) 1998-06-15
CA2240644A1 (en) 1997-06-26

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