GB865321A - Method for the preparation of alpha-fluorinated organic compounds from active hydrogen compounds - Google Patents

Method for the preparation of alpha-fluorinated organic compounds from active hydrogen compounds

Info

Publication number
GB865321A
GB865321A GB30363/58A GB3036358A GB865321A GB 865321 A GB865321 A GB 865321A GB 30363/58 A GB30363/58 A GB 30363/58A GB 3036358 A GB3036358 A GB 3036358A GB 865321 A GB865321 A GB 865321A
Authority
GB
United Kingdom
Prior art keywords
diethyl
compounds
ethyl
active hydrogen
fluoro
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.)
Expired
Application number
GB30363/58A
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.)
Pennwalt Corp
Original Assignee
Pennsalt Chemical Corp
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 Pennsalt Chemical Corp filed Critical Pennsalt Chemical Corp
Publication of GB865321A publication Critical patent/GB865321A/en
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/49—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups
    • C07C205/50—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C205/51—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by carboxyl groups having nitro groups and carboxyl groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B39/00—Halogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • 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
    • C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/16—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of hydrazones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/63—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • 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
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C07D239/62—Barbituric acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • 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
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/02—Ortho- or ortho- and peri-condensed systems
    • C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
    • C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
    • C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
    • C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
    • C07C2603/18—Fluorenes; Hydrogenated fluorenes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention comprises the compounds diethyl 2, 2-difluoromalonate, ethyl 2, 2-difluoroacetoacetate, diethyl 2-ethyl- and 2-phenyl-2-fluoromalonate, and 3, 3-difluoro-2, 4-pentanedione and its mono-2, 4-dinitro-phenylhydrazone; and a method for the preparation of a -fluorinated organic compounds by bringing together at a suitable temperature perchloryl fluoride ClO3F and an alkali metal derivative of an active hydrogen compound in which at least one active hydrogen atom has been replaced by an alkali metal atom, or the components of said derivative, namely an active hydrogen compound and an alkali metal base. An "active hydrogen compound" is defined as an organic compound containing a carbon atom to which is attached at least one hydrocarbon atom and at least one electron-accepting group. The corresponding compounds in which H is replaced by F are called "a -fluorinated compounds." An 'alkali metal base" is defined as any alkali metal compound which is sufficiently basic to remove the a -hydrogen atom from the starting compound, such as the alkoxides, hydroxide, hydride or amide, or the alkali metals themselves. Suitable active hydrogen compounds are those of the formula HCRR1R2, where R is hydrogen or a C1-12 aliphatic hydrocarbon or halogenohydrocarbon group, or a group sufficiently electronegative to render the compound capable of forming an alkali metal derivative, and R1 and R2 are separately or together such electronegative groups; specified electronegative groups are-CN, -CO.R3, -CR3=CR4R5, -COOR3, -CS.R3, -NO2 and <FORM:0865321/IV (b)/1> where R3, R4 and R5 represent hydrogen, halogen, phenyl, or a C1-3 aliphatic hydrocarbon or halogenohydrocarbon group. Examples of active hydrogen compounds are b -diketones, b -keto-esters, b -diesters, b -thioketo-esters, nitriles, nitroalkanes and cycloalkadiene compounds. Non-aqueous solvents may be used in the reaction. In Examples, the following compounds are prepared: (1) diethyl 2, 2-difluoromalonate; (2) ethyl 2, 2-difluoroacetoacetate and its 2, 4-dinitrophenylhydrazone; (3) diethyl 2-ethyl-2-fluoromalonate; (4) difluoromalonitrile; (5) methyl ethyl 2, 2-difluoromalonate; (6) a , a -difluoro-cyanoacetic acid; (7) ethyl a , a -difluoro-cyanoacetate; (8) C3H7OCOCF(CH3)COOCH2Cl; (9) CH3OCO CF2CO.CH3CH2CHCl2; (10) propyl 2, 2-difluoroacetoacetate; (11) diethyl 2-fluoro-2-(p-chlorophenyl)-malonate; (12) diethyl 2-fluoro-2-aceto-malonate; (13) diethyl 2-fluoro-2-allylo-malonate; (14) methyl a , a -difluoro-nitroacetate; (15) a -cyanoa , a -difluorotoluene; (16) 9, 9-difluorofluorene; (17) 5, 5-difluorocyclopentadiene (18) 1, 1-difluoroindane; (19) and (21) CH3COCF2COCH3; (20) CH3O.CS.CF2.CS.OCH3; (22) diethyl-2-fluoro-2-phenyl malonate. 5-Ethyl-5-fluoro-barbituric acid is prepared by reacting diethyl 2-fluoro-2-ethylmalonate with urea. Difluoromalonamide is prepared by the action of ammonia on diethyl 2, 2-difluoromalonate.
GB30363/58A 1957-09-24 1958-09-23 Method for the preparation of alpha-fluorinated organic compounds from active hydrogen compounds Expired GB865321A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US68580757A 1957-09-24 1957-09-24

Publications (1)

Publication Number Publication Date
GB865321A true GB865321A (en) 1961-04-12

Family

ID=24753748

Family Applications (1)

Application Number Title Priority Date Filing Date
GB30363/58A Expired GB865321A (en) 1957-09-24 1958-09-23 Method for the preparation of alpha-fluorinated organic compounds from active hydrogen compounds

Country Status (4)

Country Link
CH (1) CH385807A (en)
DE (1) DE1132905B (en)
FR (1) FR1212245A (en)
GB (1) GB865321A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2191843B (en) * 1986-06-12 1989-12-20 Hollingsworth Uk Ltd Vibration damper

Also Published As

Publication number Publication date
FR1212245A (en) 1960-03-22
DE1132905B (en) 1962-07-12
CH385807A (en) 1964-12-31

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