GB2255775A - 1 - fluorocyclopropane carbonyl fluoride - Google Patents

1 - fluorocyclopropane carbonyl fluoride Download PDF

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Publication number
GB2255775A
GB2255775A GB9207856A GB9207856A GB2255775A GB 2255775 A GB2255775 A GB 2255775A GB 9207856 A GB9207856 A GB 9207856A GB 9207856 A GB9207856 A GB 9207856A GB 2255775 A GB2255775 A GB 2255775A
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Prior art keywords
compound
formula
fluorocyclopropane
carbonyl fluoride
chloride
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GB9207856A
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GB9207856D0 (en
Inventor
Dr David Bartholomew
Mark Rex Spyvee
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Imperial Chemical Industries Ltd
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Imperial Chemical Industries Ltd
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    • 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
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C61/15—Saturated compounds containing halogen

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

1-Fluorocyclopropane carbonyl fluoride, its preparation by reacting 4-chloro-2-fluorobutanoyl chloride with an alkali metal fluoride and its use in the preparation of 1-fluorocyclopropane carboxamides.

Description

1-FLUOROCYCLOPROPANE CARBONYL FLUORIDE This invention relates to 1-fluorocyclopropane carbonyl fluoride, to processes for preparing it and to its use as an intermediate in the preparation of agrochemicals.
The present invention provides 1-fluorocyclopropane carbonyl fluoride.
The invention also provides a process for the preparation of 1-fluorocyclopropane carbonyl fluoride, comprising reacting 4-chloro-2-fluorobutanoyl chloride with an alkali metal fluoride in a suitable solvent at a suitable temperature.
In one aspect the process of the invention comprises the steps of: a) reacting 2-fluoro-4-butanolide with zinc (II) chloride and a suitable sulphur chloride at a suitable temperature to form a product (4-chloro-2-fluorobutanoyl chloride); and, b) reacting the product of step (a) with an alkali metal fluoride in a suitable solvent at a suitable temperature.
The invention further provides the use of 1-fluorocyclopropane carbonyl fluoride as an intermediate in the preparation of agrochemicals of formula (IV). Thus it provides a process for the preparation of a compound of formula (IV), wherein R is methoxy, chlorine or fluorine, the process comprising reacting a compound of formula (V), wherein R is as defined above, with 1-fluorocyclopropane carbonyl fluoride in a suitable solvent and in the presence of a suitable base.
The processes of the invention are shown diagrammatically in Scheme I.
In Scheme I the variable R is as defined above.
1-Fluorocyclopropane carbonyl fluoride [the compound of formula (I)] is prepared by reacting 4-chloro-2-fluorobutanoyl chloride [the compound of formula (II)1 with an alkali metal fluoride (for example potassium fluoride) in a suitable solvent that is inert under the reaction conditions (for example sulpholane) at a suitable temperature (preferably in the range 150 to 2500C).
4-Chloro-2-fluorobutanoyl chloride [the compound of formula (II)] is prepared by reacting 2-fluoro-4-butanolide [the compound of formula (III)] with zinc (II) chloride (which is preferably anhydrous) and a suitable sulphur chloride (for example thionyl chloride) at a suitable temperature (for example, in the range of 50-1000C or at the reflux). It is preferred that this reaction is carried out in the absence of a solvent.
The compound of general formula (IV) is prepared by reacting a compound of general formula (V) with 1-fluorocyclopropane carbonyl fluoride [the compound of formula (I)] in a suitable solvent (for example diethyl ether), in the presence of a suitable base (for example triethylamine) at a suitable temperature (preferably in the range -30 to 500C, for example, in the range -20 to 1000) Compounds of formula (IV) are fungicides (see European Patent Application No 90313836.0).
EXAMPLES The following Examples illustrate the invention. Where shown, NMR data are selective, no attempt is made to list every absorption. The following abbreviations are used throughout: dt = doublet of triplets c = multiplet s = singlet ddd = doublet of doublet of doublets d = doublet dd = doublet of doublets brs = broad singlet Preparation of 2-fluoro-4-butanolide [compound of formula (III)].
To a mixture of 2-hydroxy-4-butanolide (28.79g) in dry dichloromethane (150ml), at -700C, under dry nitrogen, was added diethylaminosulphur trifluoride (50g), dropwise, via a pressure equallising dropping funnel, over 80 minutes. The exotherm during addition was controlled such that the temperature of the reaction mixture was maintained below -600C. On complete addition the reaction mixture was allowed to warm to room temperature and left to stand for about 20 hours.
The reaction mixture was cautiously poured onto ice chips (lOOg). The resultant mixture was transferred to a separating funnel and the organic layer isolated. The aqueous layer was extracted with dichloromethane (3 x 150 ml). The combined organic extracts were washed with saturated sodium bicarbonate solution (200ml) and dried over magnesium sulphate.
Filtration, followed by rotary evaporation of the solvent, under reduced pressure at 400C, afforded the title compound as a brown oil (29.06g, 99 yield).
1H NMR (CDCl3) s : 2.40-2.80(c,2H); 4.20-4.60(c,2H); 5.20(dd,lH, J=8Hz, J=52Hz) ppm.
Preparation of 4-chloro-2-fluorobutanoyl chloride [compound of formula (it)1.
A mixture of 2-fluoro-4-butanolide [compound of formula (III)] (5g), zinc chloride (anhydrous) (6.55g) and thionyl chloride (10 ml) was heated under reflux for 411 hours.
The reaction mixture was distilled at atmospheric pressure to remove excess thionyl chloride. The residue was distilled in vacuo (1150C at 165 mm Hg) to afford the title compound as light green liquid (5.54g, 73t yield).
1H NMR (CDC13) : 6 2.37-2.60(c,2H); 3.67-3.80(c,2H); 5.30(ddd,lH, J=3.63Hz, J=12.34Hz, Jut48.63) ppm.
IR pC o is 1796cm Preparation of 1-fluorocyclopropane carbonyl fluoride [compound of formula (I)1.
To a well stirred suspension of dry potassium fluoride (8.75g) in dry sulpholane (28 ml), at 2000C, under a light stream of nitrogen, was added 4-chloro-2-fluorobutanoyl chloride [compound of formula (II)] (4g), dropwise over two minutes. The reaction mixture temperature rose to 2150C and a colourless distillate was collected, in a dry ice cooled receiver over about twenty minutes. The still head temperature varied from 80-1200C during distillation. The distillate was the title compound (0.85g, 32% yield).
1H NMR (CDCl3): 6 1.50-1.70(c) ppm.
IR uC=O is 1846cam 1 Preparation of 5-(2-methoxypyridyl)-1-fluorocyclopropane carboxamide [a compound of formula (IV)l.
To a solution of freshly distilled 5-amino-2-methoxypyridine (1.56g) in dry diethyl ether (5ml) was added triethylamine (1.75 ml). The mixture was cooled to -200C using a dry ice/ethylene glycol cooling bath. A solution of 1-fluorocyclopropane carbonyl fluroide [compound of formula (I)] (1.33g) in dry diethyl ether (10ml) was added dropwise, over about five minutes. The temperature of the reaction mixture was maintained below -150C during addition. On complete addition the reaction mixture was allowed to warm to room temperature. The reaction mixture was stirred at room temperture for one hour then poured into water (50 ml) and extracted with diethyl ether (3x50 ml). The combined organic extracts were washed with saturated brine solution (50 ml), and dried over magnesium sulphate.
Filtration followed by rotary evaporation of the solvent under reduced pressure at 400C afforded a tacky white solid (3.05g). Residual triethylamine was removed by high vacuum (0.1 mBar) at room temperature.
The white solid was triturated with cold (OOC) hexane and filtered off.
The solid was dried under suction to afford the title compound as a dry, white crystalline solid (2.51g). The filtrate was evaporated by rotary evaporation under reduced pressure at 40 C to afford a yellow oil (330mg) which crystallized on standing. The yellow material was recrystallized from n-hexane/diethyl ether to afford the title compound as a white crystalline solid (124mg) which was filtered off and dried. Total yield 2.634g (100X). Melting point : 121-1220C. 1H NMR (CDCl3): 6 1.33-1.53(c,4H); 3.93(s,3H); 6.77(d,1H, J=9.43Hz); 7.93(dd,lH, J=2.90Hz, J=9.43Hz); 7.97(brs,lH); 8.23(d,lH, J=2.90Hz) ppm.
MS: m/z = 211 (MH+).
Scheme I

Claims (3)

  1. CLAIMS 1. 1-Fluorocyclopropane carbonyl fluoride.
  2. 2. A process for the preparation of 1-fluorocyclopropane carbonyl fluoride comprising reacting 4-chloro-2-fluorobutanoyl chloride with an alkali metal fluoride.
  3. 3. A process for preparing a compound of formula (IV):
    wherein R is methoxy, chloro or fluoro, the process comprising reacting a compound of formula (V):
    wherein R is as defined above, with 1-fluorocyclopropane carbonyl fluoride.
GB9207856A 1991-05-15 1992-04-09 1 - fluorocyclopropane carbonyl fluoride Withdrawn GB2255775A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB919110475A GB9110475D0 (en) 1991-05-15 1991-05-15 1-fluorocyclopropane carbonyl fluoride

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GB9207856D0 GB9207856D0 (en) 1992-05-27
GB2255775A true GB2255775A (en) 1992-11-18

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GB9207856A Withdrawn GB2255775A (en) 1991-05-15 1992-04-09 1 - fluorocyclopropane carbonyl fluoride

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592001A (en) * 2014-12-30 2015-05-06 湖北博凯医药科技有限公司 Process method for synthesizing and purifying 4-chlorobutyryl chloride

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0436348A2 (en) * 1990-01-04 1991-07-10 Zeneca Limited Pyridyl cyclopropane derivatives with fungicidal activity

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0436348A2 (en) * 1990-01-04 1991-07-10 Zeneca Limited Pyridyl cyclopropane derivatives with fungicidal activity

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104592001A (en) * 2014-12-30 2015-05-06 湖北博凯医药科技有限公司 Process method for synthesizing and purifying 4-chlorobutyryl chloride

Also Published As

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GB9207856D0 (en) 1992-05-27
AU1597492A (en) 1992-11-19
GB9110475D0 (en) 1991-07-03
AU641862B2 (en) 1993-09-30

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