Classifications

• • 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
  • C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
  • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
  • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2602/00—Systems containing two condensed rings
  • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
  • C07C2602/14—All rings being cycloaliphatic
  • C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
  • C07C2602/28—Hydrogenated naphthalenes

Definitions

• the present invention relates to a process for the preparation of nitroalkenes and, more particularly, it relates to a process for the preparation of conjugated ⁇ -nitroalkenes by reaction of a conjugated alkene with a nitrite in the presence of iodine and of an oxidising agent.
• Conjugated ⁇ -nitroalkenes are widely used synthetic intermediates because they can be easily converted into a variety of different compounds. For example, we can cite ⁇ -nitrostyrene, useful intermediate for the preparation of several phenylethylamines and fungicides (Chemical Abstracts, vol. 118, no.
• Wing-Wah Sy et al [Tetr. Lett., 1985, 26(9), pages 1193-1196] describe the nitration of substituted alkenes with silver nitrite and iodine, the only difference from Hassner et al being the use of a higher molar amount of silver nitrite, which is then equimolar with respect to the iodine.
• Jew et al. replace silver nitrite with sodium nitrite and use 2 moles of iodine and 4 moles of nitrite per mole of styrene, respectively.
• potassium nitrite is used in the presence of a phase transfer catalyst and by treating with ultrasounds in order to increase the solubility of the nitrite ion.
• Different amounts of iodine were evaluated to optimise the yield and the reported general method foresees the use of 2.6 moles of nitrite and 2.75 moles of iodine per mole of alkene, respectively.
• object of the present invention is a process for the nitration of conjugated alkenes of formula
• R is a hydrogen atom, an optionally substituted phenyl, a linear or branched C 1 -C 4 alkyl
• R 1 is a hydrogen atom or a linear or branched C 1 -C 4 alkyl, optionally substituted by an OH or C 1 -C 4 alkoxy group
• R 2 , R 3 and R 4 are selected among hydrogen and halogen atoms, linear or branched C 1 -C 4 alkyl or alkoxy groups, carboxylic groups, aminocarbonyl groups, alkyloxycarbonyl, alkylcarbonyl, mono- or di-alkylaminocarbonyl alkylcarbonylamino and alkylcarbonyloxy groups having from 1 to 4 carbon atoms in the alkyl moiety; or two of R 2 , R 3 and R 4 , in ortho between them, form a methylendioxy group; or R 1 together with R 2 forms a cyclic system with 5-7 terms conden
• the nitrating agent is a mixture of an inorganic nitrite and iodine in the presence of an oxidising agent.
• the nitration process object of the present invention allows to obtain ⁇ -nitroalkenes under mild conditions with good yields.
• linear or branched C 1 -C 4 alkyl means an alkyl selected among methyl, ethyl, n-propyl, isopropyl n-butyl sec-butyl isobutyl and t-butyl;
• linear or branched C 1 -C 4 alkoxy means a group selected among methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy and t-butoxy;
• halogen means fluorine, chlorine, bromine and iodine.
• Substituted phenyl means a phenyl substituted by one or more substituents selected among the meanings of R 2 , R 3 and R 4 .
• Preferred examples of the compounds of formula I are styrenes optionally substituted on the aromatic ring by from 1 to 3 methoxy groups or by a methylenedioxy group, dihydronaphthalenes optionally substituted by methoxy, methyl, ethyl, fluoro, chloro, bromo, iodo, carboxy, methoxycarbonyl groups or by a methylenedioxy group or benzopyranes optionally substituted by methoxy, methyl, ethyl, fluoro, chloro, bromo, iodo, carboxy, methoxycarbonyl, aminocarbonyl or methylaminocarbonyl groups.
• R 3A and R 4A are hydrogen atoms, methoxy, methyl, ethyl, fluoro, chloro, bromo, iodo, carboxy, methoxycarbonyl groups or, together, form a methylenedioxy group; R has the already reported meanings;
• R 3B and R 4B are hydrogen atoms, methoxy, methyl, ethyl, fluoro, chloro, bromo, iodo, carboxy, methoxycarbonyl, aminocarbonyl or methylaminocarbonyl groups; R has the already reported meanings;
• R, R 3A , R 3B , R 4A and R 4B have the already reported meanings.
• Examples of inorganic nitrites which can be used in the process object of the present invention are silver nitrite, sodium nitrite and potassium nitrite.
• the amount of nitrite is in excess with respect to the compound of formula I, generally not lower Man 2 moles per mole of compound to be nitrated.
• nitrite from 2 and 4 moles per mole of compound of formula I is used.
• the most characterizing feature of the present process is represented by the amount of iodine which is used.
• an oxidising agent allows to significantly decrease the amount of iodine up to an amount generally equal or lower than 1 mole per mole of compound of formula I, preferably from 0.1 and 0.8 moles per mole of substrate to be nitrated.
• the oxidation agent is slowly added, usually in 34 hours, to the reaction mixture containing the nitrite, iodine and the compound of formula I.
• AlkH represents the compound of formula I
• a further stage is represented by the fact that, by using an oxidising agent, the iodine can also be prepared in situ by oxidation of iodides.
• Iodides which can be used for such purposes are generally alkali metal iodides, preferably potassium iodide.
• oxidising agents which can be used in the process object of the present invention are peracids such as peracetic acid and m-chloroperbenzoic acid, oxygen peroxide and inorganic nitrites, optionally in admixture each other.
• the oxidising agent must be used in an acid environment, preferably at a pH lower than 5.
• the amount of oxidant will be in relation to the used amount of iodine, preferably in slight excess.
• a higher amount of oxidant will be needed to allow the initial oxidation of the iodides
• the process object of the present invention is carried out in the presence of a suitable organic solvent which is selected in relation to the solubility of the compound of formula I but which is not a critical parameter for the achievement of the process.
• esters such as ethyl acetate, isopropyl acetate and isobutyl acetate
• aromatic hydrocarbons such as toluene and xylene
• chlorinated hydrocarbons such as methylene chloride and 1,2-dichloropropane
• ethers such as tert-butyl methyl ether.
• reaction mixture contains water
• addition of a phase transfer catalyst can be. useful.
• the temperature is not a critical parameter. Preferably temperatures from 20° C. to 70° C. are used. A still more preferred temperature range is from 40° C. to 50° C.
• a preferred embodiment of the process object of the present invention is the following.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Pyrane Compounds (AREA)

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• 2001
  • 2001-06-19 EP EP01956483A patent/EP1294658B1/fr not_active Expired - Lifetime
  • 2001-06-19 CN CNB018116868A patent/CN1232480C/zh not_active Expired - Fee Related
  • 2001-06-19 DE DE60109163T patent/DE60109163T2/de not_active Expired - Lifetime
  • 2001-06-19 CA CA2412232A patent/CA2412232C/fr not_active Expired - Lifetime
  • 2001-06-19 ES ES01956483T patent/ES2239155T3/es not_active Expired - Lifetime
  • 2001-06-19 AT AT01956483T patent/ATE289986T1/de active
  • 2001-06-19 DK DK01956483T patent/DK1294658T3/da active
  • 2001-06-19 WO PCT/EP2001/006902 patent/WO2002000575A1/fr active IP Right Grant
  • 2001-06-19 JP JP2002505326A patent/JP4705307B2/ja not_active Expired - Fee Related
  • 2001-06-19 US US10/311,319 patent/US20040006248A1/en not_active Abandoned
  • 2001-06-19 PT PT01956483T patent/PT1294658E/pt unknown
  • 2001-06-19 AU AU2001278456A patent/AU2001278456A1/en not_active Abandoned
• 2005
  • 2005-10-12 US US11/247,600 patent/US7265251B2/en not_active Expired - Fee Related

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