Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
  • C07F7/1804—Compounds having Si-O-C linkages
  • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
  • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C17/00—Preparation of halogenated hydrocarbons
  • C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
  • C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
  • C07C49/233—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings
  • C07C49/235—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen containing six-membered aromatic rings having unsaturation outside the aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/527—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings
  • C07C49/567—Unsaturated compounds containing keto groups bound to rings other than six-membered aromatic rings containing halogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C67/00—Preparation of carboxylic acid esters
  • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
  • C07C67/293—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
• • 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
  • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
  • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
  • C07C67/347—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
• • 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
  • C07C2602/20—All rings being cycloaliphatic the ring system containing seven carbon atoms

Definitions

• the present invention relates to a method for producing a difluorocyclopropane compound. More specifically, the present invention relates to a method for producing a difluorocyclopropane compound useful as an intermediate for pharmaceuticals or agricultural chemicals.
• Non-Patent Documents 1 and 2 compounds having a difluorocyclopropane skeleton have attracted attention in the fields of medicine, agricultural chemicals, and material chemistry.
• gem-difluorocyclopropane compounds have specific biological activities such as anti-cancer action and DNA cleavage action. Recently, they have been used for biological constituent molecules such as nucleosides and amino acids, liquid crystals, and polymer materials. Research into the introduction of gem-difluorocyclopropane skeletons is also underway.
• many examples of applications using difluorocyclopropanes have been reported, such as studies on the conversion of difluorocyclopropanes into various difluoromethylene compounds using ring cleavage reactions.
• the problem to be solved by the present invention is to provide a method for producing a difluorocyclopropane compound with a high selectivity and a high yield under milder reaction conditions. It is another object of the present invention to provide a method for producing a difluorocyclopropane compound having various functional groups, which can be easily treated after the reaction (has no hazardous waste).
• the present inventor has intensively studied to solve the above problems. As a result, it has been found that if sodium bromodifluoroacetate is used as the difluorocyclopropanating agent, a method for producing a difluorocyclopropane compound with high selectivity and high yield capable of solving the above-described problems can be provided.
• the conventional method using chlorodifluoroacetate does not necessarily have a high conversion rate (conversion rate: about 60%), and even when actually producing a difluorocyclopropane compound, the reaction does not easily progress in the middle. It was very difficult to separate the product from the raw material remaining in the reaction system. This is supported by the fact that a number of by-products other than the target product are likely to be produced by an experimental example using sodium chlorodifluoroacetate (a comparative example described later).
• Non-Patent Document 8 it is also known that sodium bromodifluoroacetate tends to cause thermal decomposition at a lower temperature than sodium chlorodifluoroacetate. For this reason, even if sodium bromodifluoroacetate is used as a difluorocyclopropanating agent in the production of a difluorocyclopropane compound, those skilled in the art have a low conversion rate as in the case of using sodium chlorodifluoroacetate. Moreover, it was naturally expected that the yield would be low.
• the present inventors actually produced a difluorocyclopropane compound using sodium bromodifluoroacetate, surprisingly, the selectivity was extremely high compared with the case where sodium chlorodifluoroacetate was used ( It was found that the desired product can be obtained with a conversion rate and yield. The present inventors have also found that the target product can be obtained in a higher yield by carrying out the reaction using sodium bromodifluoroacetate under certain reaction conditions.
• the present invention is as follows.
• a method for producing a difluorocyclopropane compound by reacting a compound having a chain or cyclic ethylene skeleton or a derivative thereof with a difluorocyclopropanating agent bromodifluoroacetate is used as the difluorocyclopropanating agent, Said method.
• examples of the compound having an ethylene skeleton or a derivative thereof include the following general formula (1):
• R 1 to R 4 are each independently a hydrogen atom or a linear or branched chain having 1 to 10 carbon atoms which may be substituted with any group. It represents an aliphatic hydrocarbon group, an aromatic ring group, an alkoxy group, an alkoxycarbonyl group, a trialkylsilyl group or a boryl group.
• R 2 and R 4 may form part of the same aliphatic ring or aliphatic heterocyclic ring, or may form a single bond with each other.
• examples of the difluorocyclopropane compound include the following general formula (2): [In general formula (2), R 1 to R 4 are the same as above. ] The compound represented by these is mentioned.
• examples of the bromodifluoroacetate include the following formula: BrCF 2 CO 2 R 5 (In the formula, R 5 represents an alkali metal atom or an alkaline earth metal atom.) The thing represented by is mentioned.
• examples of the alkali metal include sodium, lithium and potassium, and examples of the alkaline earth metal include magnesium.
• the reaction temperature of the reaction can be, for example, 100 to 200 ° C.
• the reaction time of the reaction can be, for example, 5 to 60 minutes.
• the production method of the present invention is an extremely practical and useful method because it can be easily industrially implemented (adopted on an industrial scale).
• bromodifluoroacetate as a difluorocyclopropanating agent is inexpensive and easily available, and is relatively easy to handle (for example, sodium chlorodifluoroacetate has some deliquescent properties due to moisture absorption and is somewhat handled.
• sodium bromodifluoroacetate does not show any deliquescent properties), and the production method of the present invention can be said to be useful.
• the method for producing a difluorocyclopropane compound according to the present invention is characterized in that bromodifluoroacetate is used as the difluorocyclopropanating agent. More specifically, the production method of the present invention is a method for producing a difluorocyclopropane compound by reacting a compound having a chain or cyclic ethylene skeleton or a derivative thereof with a difluorocyclopropanating agent. As described above, bromodifluoroacetate is used as the difluorocyclopropanating agent.
• the difluorocyclopropane compound obtained by the production method of the present invention is not limited to difluorocyclopropane, but includes all compounds containing a skeleton structure derived from difluorocyclopropane in the chemical structure. That is, the difluorocyclopropane compound referred to in the present invention is meant to include all difluorocyclopropane compounds and difluorocyclopropane compound derivatives which may be substituted with an arbitrary group.
• difluorocyclopropane compound in the present invention include compounds represented by the following general formula (2).
• R 1 to R 4 are not limited, but are independently of each other, for example, a hydrogen atom or an optionally substituted group having 1 to 1 carbon atoms. 10 linear or branched aliphatic hydrocarbon groups, aromatic ring groups, alkoxy groups, alkoxycarbonyl groups, trialkylsilyl groups, or boryl groups are represented.
• the “aliphatic hydrocarbon group” may be either saturated or unsaturated, and is not limited, and examples thereof include alkyl groups, alkenyl groups, alkynyl groups, and two or more carbon-carbon unsaturated double groups. Examples thereof include an unsaturated aliphatic hydrocarbon group having a bond and / or a triple bond.
• the hydrogen atoms bonded to any carbon atom of the hydrocarbon group are each independently of each other, for example, a halogen atom, a straight chain having 1 to 10 carbon atoms, or A branched alkoxy group, a linear or branched haloalkoxy group having 1 to 10 carbon atoms, a linear or branched alkylamino group having 1 to 10 carbon atoms, a linear chain having 1 to 10 carbon atoms, or Branched alkylthio group, cyano group, aminocarbonyl group (CONH 2 ), aromatic ring group, nucleobase, aromatic ring oxy group, aliphatic heterocyclic group, protected hydroxyl group, protected amino group, and carboxyl It may be substituted in any number and combination with a group selected from a group protector and the like.
• aromatic ring group examples include, but are not limited to, an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, and an anthryl group, and a furyl group, a pyrrolyl group, a thienyl group, a benzofuryl group, an indolyl group, and a benzothienyl group.
• aromatic hydrocarbon groups and aromatic heterocyclic groups are, for example, linear or branched alkyl groups having 1 to 10 carbon atoms, halogen atoms, linear or branched chain groups having 1 to 10 carbon atoms.
• An amino group protector, a carboxyl group protector and the like may be substituted.
• alkoxy group is not limited, and examples thereof include linear or branched alkoxy groups having 1 to 10 carbon atoms, aromatic ether groups, trialkylsiloxy groups, and acyloxy groups.
• alkoxycarbonyl group include, but are not limited to, an alkoxycarbonyl group composed of a linear or branched alkoxy group having 1 to 10 carbon atoms.
• the “trialkylsilyl group” is not limited, and examples thereof include a trimethylsilyl group and a triethylsilyl group.
• the “boryl group” is not limited, and examples thereof include a di (alkoxy) boryl group and a dialkylboryl group.
• examples of the “halogen atom” include atoms such as fluorine, chlorine, bromine and iodine.
• examples of the “linear or branched alkoxy group having 1 to 10 carbon atoms” include a methoxy group, an ethoxy group, a propoxy group, and the like.
• examples of the “C1-C10 linear or branched haloalkoxy group” include a fluoromethoxy group, a chloromethoxy group, a bromomethoxy group, and the like.
• Examples of the “C1-C10 linear or branched alkylamino group” include a dimethylamino group, a diethylamino group, a dipropylamino group, and the like.
• Examples of the “C1-C10 linear or branched alkylthio group” include a methylthio group, an ethylthio group, a propylthio group, and the like.
• Examples of the “nucleobase” include adenine residue, guanine residue, hypoxanthine residue, xanthine residue, uracil residue, thymine residue, cytosine residue and the like.
• Examples of the “aromatic oxy group” include a phenoxy group and a naphthoxy group.
• Examples of the “aliphatic heterocyclic group” include piperidyl group, piperidino group, morpholinyl group and the like.
• Examples of the “protector for hydroxyl group, protector for amino group, and protector for carboxyl group” include, for example, Protective Groups in Organic Synthesis, Third Edition, 1999, John Wiley & Sons, Inc. Can be used.
• examples of the “hydroxyl group protector” include a trityl group (triphenylmethyl group), a tetrahydropyranyl group (THP group), a tetrahydrofuranyl group (THF group), and the like.
• Examples of the “protected amino group” include benzyloxycarbonyl group, tert-butoxycarbonyl (Boc) group, 9-fluorenylmethoxycarbonyl (Fmoc) group, 3-nitro-2-pyridinesulfenyl (Npys) Group, p-methoxybenzyloxycarbonyl [Z (MeO)] group and the like.
• Examples of the “protector of carboxyl group” include methyl (Me) group, ethyl (Et) group, tert-butyl (t-Bu) group, trichloroethyl (Tce) group, phenacyl (Pac) group, benzyl (Bzl). ) Group, 4-nitrobenzyl [Bzl (4-NO 2 )] group, 4-methoxybenzyl [Bzl (4-MeO)] group and the like.
• R 2 and R 4 may be R 1 and R 3 ) constitute part of the same aliphatic ring. Also good. Specifically, for example, when R 2 and R 4 are the above-described aliphatic hydrocarbon groups (especially alkyl groups), any carbon atom in the hydrocarbon group is bonded to form a cyclic structure. The aspect which comprises a part and comprises an aliphatic ring is mentioned. In another embodiment, R 2 and R 4 may form part of the same aliphatic heterocycle.
• Examples of the aliphatic heterocyclic ring include those having a cyclic skeleton in which a part of carbon atoms constituting the cyclic skeleton of the aliphatic ring is substituted with a nitrogen atom or an oxygen atom.
• R 2 and R 4 may be R 1 and R 3 ) may form a single bond with each other.
• a carbon atom other than the carbon atom to which two fluorine atoms are bonded among the carbon atoms constituting the cyclopropane ring may be an asymmetric carbon atom.
• R 2 and R 4 in the general formula (2) may be R 1 and R 3 ) may form a single bond with each other.
• the following general formula A compound represented by (2 ′) can be exemplified.
• the compound represented by the general formula (2 ′) can be referred to as a derivative of the difluorocyclopropane compound represented by the general formula (2).
• R 2 and R 4 in the general formula (2) may be R 1 and R 3 ) may form part of the same aliphatic ring.
• R 2 and R 4 are the above-described aliphatic hydrocarbon groups (especially alkyl groups)
• any carbon atom in the hydrocarbon group is bonded to form a cyclic structure.
• the aspect which comprises a part and comprises an aliphatic ring is mentioned,
• the compound etc. which are represented with the following general formula (2 '') can be illustrated.
• the compound represented by the general formula (2 ′′) can be referred to as a derivative of the difluorocyclopropane compound represented by the general formula (2).
• R 2 and R 4 are preferably, for example, each independently a methylene group that may be substituted with any group.
• R 2 and R 4 in the general formula (2) may form part of the same aliphatic heterocycle.
• the aliphatic heterocyclic ring include those having a cyclic skeleton in which a part of carbon atoms constituting the cyclic skeleton of the aliphatic ring is substituted with a nitrogen atom or an oxygen atom.
• Preferred specific examples of the compound represented by the general formula (2) and derivatives thereof include various difluorocyclopropanes produced in the examples described later.
• the difluorocyclopropane compound and derivatives thereof obtained by the production method of the present invention are not limited, but are preferably optically active and meso forms.
• the compound having a chain or cyclic ethylene skeleton (carbon-carbon unsaturated double bond) used as a raw material compound in the production method of the present invention is not limited, and the ethylene skeleton (ethylene group) in the chemical structure is not limited. All chain-like or cyclic compounds containing a skeleton structure) and derivatives thereof are included.
• Examples of the compound having an ethylene skeleton in the present invention include compounds represented by the following general formula (1).
• R 1 to R 4 are the same as described above (that is, the same as described in the description of the general formula (2)).
• R 2 and R 4 in the general formula (1) may be R 1 and R 3 ) may form a single bond with each other.
• the following general formula A compound represented by (1 ′) can be exemplified.
• the compound represented by the general formula (1 ′) is a compound having an acetylene skeleton (carbon-carbon unsaturated triple bond) as a result of R 2 and R 4 forming a single bond.
• a derivative of a compound having an ethylene skeleton represented by the general formula (1) is exemplified.
• R 2 and R 4 in the general formula (1) may be R 1 and R 3 ) may form part of the same aliphatic ring.
• R 2 and R 4 are the above-described aliphatic hydrocarbon groups (especially alkyl groups)
• any carbon atom in the hydrocarbon group is bonded to form a cyclic structure.
• the aspect which comprises a part and comprises an aliphatic ring is mentioned,
• the compound etc. which are represented with the following general formula (1 '') can be illustrated.
• the compound represented by the general formula (1 ′′) can be referred to as a derivative of the difluorocyclopropane compound represented by the general formula (1).
• R 2 and R 4 are preferably, for example, each independently a methylene group that may be substituted with any group.
• R 2 and R 4 in general formula (1) may form part of the same aliphatic heterocycle.
• the aliphatic heterocyclic ring include those having a cyclic skeleton in which a part of carbon atoms constituting the cyclic skeleton of the aliphatic ring is substituted with a nitrogen atom or an oxygen atom, as described above.
• Preferred specific examples of the compound represented by the general formula (1) and derivatives thereof include an ethylene skeleton used in the examples described later. Various compounds are mentioned.
• R 5 is preferably an alkali metal atom or an alkaline earth metal atom.
• Preferred examples of the alkali metal atom include sodium, lithium, and potassium, and preferred examples of the alkaline earth metal include magnesium.
• Bromodifluoroacetate generates difluorocarbene in the reaction system, and has an action of difluorocyclopropanation on the compound having an ethylene skeleton or a derivative thereof.
• the reaction conditions between the compound having an ethylene skeleton or a derivative thereof and bromodifluoroacetate are not limited, but for example, the reaction is preferably performed under the following conditions. That is, the reaction solvent is not particularly limited as long as it is a high boiling point solvent (generally 150 ° C. or higher) generally used in organic chemical synthesis. For example, diglyme, N, N-dimethylformamide, N-methylpyrrolidone, etc. Can be preferably used.
• 0.1 L (liter) or more should just be used with respect to 1 mol of compounds expressed with General formula (1), and its derivative (s), and usually 0.1 To 20 L is preferable, and 0.1 to 10 L is more preferable.
• these organic solvents can be used individually or in combination.
• the blending ratio of the raw material compound may be appropriately set according to the type of the compound to be used, and is not limited.
• bromodifluoroacetate is used for the compound represented by the general formula (1) and its derivative. It is preferable to use 1 to 10 equivalents, and more preferably 1.2 to 8 equivalents.
• the reaction temperature of the reaction is, for example, preferably 100 to 200 ° C., more preferably 120 to 180 ° C.
• the reaction time of the reaction may vary depending on the substrate and reaction conditions and is not particularly limited. For example, it is preferably 5 to 60 minutes, more preferably 5 to 30 minutes, and still more preferably 10 to 20 minutes.
• the end point of the reaction is preferably a time point at which the progress of the reaction is tracked by an analytical means such as gas chromatography, liquid chromatography, or NMR, and the raw material is almost disappeared.
• the pressure condition of the reaction is not particularly limited, but may be, for example, in the range of normal pressure (0.1 MPa (absolute pressure reference, hereinafter the same)) to 2 MPa. In this case, 0.1 MPa to 1. 5 MPa is preferable, and 0.1 MPa to 1 MPa is particularly preferable.
• the reactor used for this process should just be what can react under normal pressure or pressurization.
• the material is not particularly limited as long as it can withstand the pressure, and a reaction in which tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass, etc. are lined inside. Or a glass container can be used.
• the reaction can also be performed while introducing an inert gas into the reactor. As the inert gas used, nitrogen gas, argon gas and the like are preferable.
• the post-treatment method is not particularly limited, and the reaction product after completion of the reaction may be treated based on a usual organic synthesis treatment method (extraction, distillation, dehydration, etc.).
• the difluorocyclopropane compound can be obtained by a usual means.
• the production method of the present invention is superior in cost and productivity because the reaction can be carried out under low temperature conditions (slow reaction conditions) as compared with conventional synthesis methods of difluorocyclopropane compounds.
• the difluorocyclopropane compound which is the target product can be obtained with a high conversion rate.
• the production method of the present invention uses, for example, bromodifluoroacetate as the difluorocyclopropanating agent, so that, for example, the dropping rate of the difluorocyclopropanating agent during the reaction can be increased compared to the conventional method. .
• the production method of the present invention is excellent in productivity.
• the difluorocyclopropane compound and its derivative obtained by the production method of the present invention have both an atomic group and an atom that can impart two specific properties of a cyclopropane ring and a fluorine atom, for example, It is useful as a physiologically active substance such as pharmaceuticals and agricultural chemicals and synthetic intermediates thereof. In the field of materials science, for example, use as a liquid crystal or a raw material thereof is also conceivable.
• 1,1-diphenylethylene compound 1a; 54.0 mg, 0.3 mmol
• diglyme 1.5 mL
• bromodifluoro is added at 150 ° C. for 10 minutes.
• a solution of sodium acetate (118 mg, 0.6 mmol) in diglyme (3.0 mL) was added dropwise, and the mixture was further stirred for 5 minutes.
• 1,2-diphenylethylene compound 1e; 18.0 mg, 0.1 mmol
• diglyme 0.5 mL
• bromodifluoro is added at 150 ° C. for 10 minutes.
• a solution of sodium acetate (157 mg, 0.8 mmol) in diglyme (1.0 mL) was added dropwise, and the mixture was further stirred for 5 minutes.
• GC / MS measurement of the solution after the reaction it was found that the target compound 2e was produced with a conversion yield of 34%.
• diphenylacetylene compound 1k; 53.5 mg, 0.3 mmol
• diglyme 3.0 mL
• sodium bromodifluoroacetate 236.4
• the reaction mixture was washed with water and dried over sodium sulfate. After distilling off the solvent under reduced pressure, the residue was purified by recrystallization (solvent was hexane-EtOAc) to obtain the objective compound 2k as a colorless solid in an isolated yield of 75% (51.7 mg).
• the production method of the present invention is an extremely practical and useful method because it can be easily industrially implemented (adopted on an industrial scale).
• bromodifluoroacetate as a difluorocyclopropanating agent is inexpensive and easily available, and is relatively easy to handle (for example, sodium chlorodifluoroacetate has some deliquescent properties due to moisture absorption and is somewhat handled.
• sodium bromodifluoroacetate does not show any deliquescent properties), and the production method of the present invention can be said to be useful.

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• 2010
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