WO2019020726A1 - Method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by heterogeneous cobalt catalysis - Google Patents
Method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by heterogeneous cobalt catalysis Download PDFInfo
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- WO2019020726A1 WO2019020726A1 PCT/EP2018/070242 EP2018070242W WO2019020726A1 WO 2019020726 A1 WO2019020726 A1 WO 2019020726A1 EP 2018070242 W EP2018070242 W EP 2018070242W WO 2019020726 A1 WO2019020726 A1 WO 2019020726A1
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- JUJWROOIHBZHMG-UHFFFAOYSA-N c1ccncc1 Chemical compound c1ccncc1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- KYQCOXFCLRTKLS-UHFFFAOYSA-N c1cnccn1 Chemical compound c1cnccn1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N c1cncnc1 Chemical compound c1cncnc1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
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- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/266—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of hydrocarbons and halogenated hydrocarbons
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- C07C17/32—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by introduction of halogenated alkyl groups into ring compounds
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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- C07C45/45—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by condensation
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- C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
- C07C45/58—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in three-membered rings
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- 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
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- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
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- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
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- 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
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- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/12—Radicals substituted by halogen atoms or nitro or nitroso radicals
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- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Definitions
- the invention discloses a method for preparation of alkylated, fluoro alkylated, chloro alkylated and fluorochloro alkylated compounds by a heterogeneous Co-catalysed alkylation or fluoro, chloro and fluorochloro alkylation with alkyl halides, fluoro alkyl halides, chloro alkyl halides or fluorochloro alkyl halides respectively.
- Organo fluorine chemistry plays an important role in medicinal, agricultural, and material sciences and fields.
- Haloalkyl groups have strong effects on the properties of compounds such as stability and lipophilicity, and in addition, long chain haloalkyl groups, in particular fluoroalkyl groups provide high water- and oil-resistance and low friction.
- homogeneous catalysis suffers from the inherent problems associated with homogeneous catalyzed reactions due to the use of unrecoverable catalysts comprising metals and ligands.
- unrecoverable catalysts comprising metals and ligands.
- inconveniences with regard to catalyst handling, recyclability, and separation of the catalyst from products impede the transfer of these approaches to large-scale industrial processes.
- expensive and structurally complicated ligands are required in homogeneous catalysis, which are often not commercially available for use on industrial scale.
- EP 0 114 359 Al discloses a process for the manufacture of perfluoralkyl substituted carbocyclic or heterocyclic compounds by reaction of perfluoroalkyl iodides with unsubstituted or substituted carbocyclic or heterocyclic compounds at elevated temperatures and in presence of at least one alkaline salt, characterized by carrying out the reaction in the presence of at least one metal of the first or eight auxiliary group of the periodic table or in the presence of a complex compound containing said metal as the central atom.
- WO 93/16969 A discloses a process for the catalytic perfluoro alkylation of aromatic compounds, wherein a perfluoroalkyl iodide or mixture of iodides is reacted with an aromatic compound in the presence of an aqueous base, such as an alkali metal hydroxide or carbonate, and discloses that further improvements in rate and yield are secured by employing, as the catalyst, a noble metal supported on porous silica microspheres.
- EP 1 947 092 Al discloses perfluoroalkylation of nucleobases with a perfluoroalkyl halide in the presence of a sulfoxide, a peroxide and an iron compound.
- a specifically mentioned catalytic system is a Fe2(S04)3/H2S04 H 2 02 system.
- WO 2015/185677 Al describes a method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by heterogeneous catalysis using a Pt/C-catalyst in the presence of CS2CO3 or CSHCO3. While the use of a Pt/C-catalyst allows for heterogeneous catalysis, Pt is an expensive metal resulting in considerable costs for the manufacturing process of alkylated or haloalkylated compounds on an industrial scale.
- the method should be applicable to a wide variety of substrates and should be compatible with a wide variety of functional groups. Furthermore the method should not be restricted to iodides as alkylating agent only, but should also work with other halides in particular with bromides. And the method should work not only with perfluorinated alkyl halides, but also with fluorinated and chlorinated alkyl halides. Furthermore, since noble metal catalysts used so far are expensive, a catalyst system which works effectively without noble metal is desired.
- a substrate herein also called COMPSUBST
- COMPSUBST is reacted in the presence of CAT with a halide, the alkylating agent, herein also called ALKHAL, to introduce an alkyl, fluoro alkyl, chloro alkyl or fluorochloro alkyl residue into COMPSUBST and thereby forming the product which is an alkylated, fluoro alkylated, chloro alkylated or fluorochloro alkylated compound, herein also called AL YLCOMPSUBST.
- AL YLCOMPSUBST alkylating agent
- Co-Ll/C as catalyst provides unexpected advantages.
- the catalyst can be reused and is not deactivated by the reaction.
- the method is applicable both to aromatic and non-aromatic compounds.
- heterocyclic compounds can be converted, even nonactivated thiophenes react smoothly at comparably low temperatures.
- a particular advantage of the method according to the invention is that not only iodides can be used as alkylating agent, that is as ALKHAL, but that also good results are obtained with bromides as alkylating agent. It was surprisingly found that also when using bromides as ALKHAL high selectivites and high yields were obtained, also with different substrates, by use of the catalyst Co- Ll/C. This has essential advantages in practice as the bromides are significantly more favorable compared to the iodides and therefore the method can be carried out much more efficiently. Further, side products emerging from the use of iodides are more difficult to dispose.
- alkyl linear or branched alkyl; preferably linear alkyl
- R34, R28 and R38 are identical or different and independently from each other selected from the group consisting of is used synonymously with "R24, R34, R28 and R38 at each occurrence are identical or different and independently from each other selected from the group consisting of
- halogen or halo F, CI, Br or I preferably F, CI or Br; more preferably F or CI;
- Co-Ll/C cobalt 1,10-phenanthroline supported on carbon, to be more precise it is cobalt oxide supported on 1,10-phenanthro line/carbon and can therefore also be abbreviated with C03O4-LI/C;
- TEA triethylamine wt%, “% by weight” and “weight-%” are used synonymously and mean percent by weight.
- Subject of the invention is a method for the preparation of an alkylated, fluoro alkylated, chloro alkylated or fluorochloro alkylated compound ALKYLCOMPSUBST with heterogeneous catalysis by a reaction of a compound COMPSUBST with an alkylating agent ALKHAL in the presence of a catalyst CAT;
- ALKHAL is a compound of formula (III);
- X is Br or I
- R3 is Ci-20 alkyl
- Ci-20 alkyl residue R3 of ALKHAL is either unsubstituted, or at least one hydrogen residue of the Ci-20 alkyl residue R3 of ALKHAL is substituted by F or CI;
- CAT is Co-Ll/C
- LI 1,10-phenanthroline
- COMPSUBST is selected from the group consisting of a compound COMPSUBST-I, compound of formula (II), compound of formula (IV), polystyrene, ethene and ethine; wherein
- COMPSUBST-I is a ring RINGA or is a RINGA condensed with a ring RINGB;
- RINGA is a 5 or 6 membered carbocyclic or heterocyclic ring
- RINGA when RINGA is a heterocyclic ring, then RINGA has 1 , 2 or 3 identical or different endocyclic heteroatoms independently from each other selected from the group consisting of N, O and S;
- RINGA when RINGA is a 5 membered ring, then RINGA is unsubstituted or substituted by 1 , 2, 3 or 4 identical or different subsitutents,
- RINGA when RINGA is a 6 membered ring then RINGA is unsubstituted or substituted by 1, 2, 3, 4 or
- any of said subsitutents of RINGA is independently from any other of said substitutent of
- RINGA selected from the group consisting of Ci-10 alkyl, C3-8 cycloalkyl, C1-4 alkoxy, OH, N(R10)R1 1 , CN, NH-OH, NO, N0 2 , F, CI, Br, I, CF 3 , (CH 2 ) m -C(0)Yl, S(O) 2 R50,
- CH C(H)R28, C ⁇ C-R24 ; benzyl, phenyl and naphthyl;
- RINGB is a 5 or 6 membered carbocyclic or heterocyclic ring, resulting in a bicyclic having 8,
- RINGB when RINGB is a heterocyclic ring, then RINGB contains 1 , 2 or 3 identical or different
- endocyclic heteroatoms independently from each other selected from the group consisting of N, O and S;
- any of said benzyl, phenyl and naphthyl substitutent of RINGA or RINGB is independently from each other unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, C1-4 alkoxy, N0 2 and CN; m and n are identical or different and independently from each other an integer from 0 to 10; wherein
- R40 and R41 are identical or different and independently from each other selected from the group consisting of -(CH 2 ) q -C(0)R13 and -CN;
- R42 is selected from the group consisting of -(CH 2 ) q -C(0)R13, -CN and R13;
- q is independently an integer from 0 to 10;
- any of the R14, R15 and R16 are identical or different and independently from each other selected from the group consisting of H, F, CI and Br; any of the RIO, Rl 1, R17, R18, R19 and R20 are identical or different and are independently from each other H or Ci-e alkyl, or RIO and Rl 1, R17 and R18 or R19 and R20 represent together tetramethylene or pentamethylene.
- X is Br.
- RINGA when RINGA is a heterocyclic ring, then RINGA has 1 , 2 or 3 identical or different endocyclic heteroatoms independently from each other selected from the group consisting of N and S.
- RINGB when RINGB is a heterocyclic ring, then RINGB contains 1, 2 or 3 identical or different endocyclic heteroatoms independently from each other selected from the group consisting of N and S.
- RINGA is an aromatic ring.
- RINGB is an aromatic ring.
- RINGA and RINGB are aromatic rings.
- COMPSUBST is selected from the group consisting of COMPSUBST-I,
- COMPSUBST-I, ethene and the ethine are as defined herein, also with all their
- COMPSUBST-I is RINGA or is RINGA condensed with RINGB and is
- COMPSUBST-I is RINGA or is RINGA condensed with RINGB and is selected from the group consisting of
- COMPSUBST-I is RINGA or is RINGA condensed with RINGB and is selected from the group consisting of
- COMPSUBST-I is RINGA or is RINGA condensed with RINGB and is selected from the group consisting of
- COMPSUBST-I is RINGA and is selected from the group consisting of
- COMPSUBST-I is RINGA and is selected from the group consisting of
- RINGA or RINGA condensed with RINGB being unsubstituted or substituted by 1, 2, 3 or 4 in case of RINGA being a monocyclic compound with 5 endocyclic atoms, by 1, 2, 3, 4 or 5 in case of RINGA being a monocyclic compound with 6 endocyclic atoms, by 1, 2, 3, 4, 5 or 6 in case of RINGA condensed with RINGB being a bicyclic compound wherein a 5-membered and a 6-membered ring are ortho-fused,
- Ci-io alkyl substitutent is unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, OH, 0-C(0)-Ci-5 alkyl, O-Ci-io alkyl, S-Ci-10 alkyl, S(0)-Ci-io alkyl, S(0 2 )-Ci-io alkyl, O-Ci-e alkylen-O-Ci-e alkyl, C3-8 cycloalkyl and 1,2,4-triazolyl;
- said benzyl, phenyl and naphthyl substitutent is independently from each other unsubstituted or substituted with 1, 2, 3, 4 or 5 identical or different substituents selected from the group consisting of halogen, CM alkoxy, N0 2 and CN;
- RIO and Rl 1 are identical or different and are independently from each other H or Ci-6 alkyl or RIO and Rl 1 represent together a tetramethylene or a pentamethylene group;
- R24 and R28 are identical or different and are independently from each other OH, Ci-io alkyl, C(R25)(R26)-0-R27, with R25, R26 and R27 being identical or different and indepedently from each other being H or C 1-10 alkyl;
- R50 is OH, Ci-6 alkyl or C 1-6 alkoxy
- Yl is H, OH, C (R14) (R15) R16, Ci-e alkyl, O-Ci 6 , phenyl, benzyl, O-phenyl, O-G 6 alkylen-O- C1-6 alkyl or N (R19) R20 with R14, R15, R16 being identical or different and independently from each other H, F, CI or Br;
- R19 and R20 being identical or different and are independently from each other H or Ci-6 alkyl or R19 and R20 represent together a tetramethylene or a pentramethylene group;
- n is independently an integer from 0 to 10.
- m, n, p and q are identical or different and independently from each other an integer 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10; more preferably at each occurence, m, n, p and q are identical or different and independently from each other an integer from 0 to 4 and in particular 0, 1, 2, 3 or 4;
- m, n, p and q are independently 0 or 4.
- Yl, Y2 and R13 are identical or different and
- Yl, Y2 and R13 are identical or different and independently from each other selected from the group consisting of H, OH, C 1-2 alkyl, and O-C1-2 alkyl.
- RINGA or RINGA condensed with RINGB is unsubstituted or substituted
- Ci-4 alkyl substitutent is unsubstituted or substituted with 1, 2 or 3 identical or different
- COMPSUBST is selected from the group consisting of benzene, pyrazole,
- Yl, RIO, Rl 1, m, R50, R28 and R24 are as defined herein, also with all their embodiments; preferably, Yl and Rl independently are Ci-6 alkyl or O- Ci-6 alkyl.
- COMPSUBST is selected from the group consisting of
- Yl, RIO, Rl 1, m, R50, R28 and R24 are as defined herein, also with all their embodiments; preferably, Yl and Rl independently are Ci-6 alkyl or O-Ci-6 alkyl.
- COMPSUBST is selected from the group consisting of
- Yl is as defined herein, also with all their embodiments; preferably, Yl is d_6 alkyl or O-Ci 6 alkyl;
- Yl is methyl, ethyl, methoxy
- COMPSUBST is selected from the group consisting of
- COMPSUBST is selected from the rou consistin of
- COMPSUBST is selected from the group consisting of
- COMPSUBST is a compound of formula (II), or a compound of formula (IV), wherein als residues are defined as above, also with all their embodiments.
- Ci-io alkyl consisting of Ci-io alkyl, C 3 -e cycloalkyl, C alkoxy, N(R10)R1 1, CN, F, CI, Br, I, CF 3 ,
- an ethine which is unsubstituted or substituted by 1 substitutent selected from the group consisting of CLIO alkyl, C 3 _ 6 cycloalkyl, C alkoxy, N(R10)R11, CN, F, CI, Br, I, CF 3 , (CH 2 ) m -C(0)Yl,
- the ethene is unsubstituted or substituted by 1 or 2 substitutents selected from the group consisting of CMO alkyl, CM alkoxy, N(R10)R11, CN, F, CI, Br, I, CF 3 , (CH 2 ) m -
- the ethine being unsubstituted or substituted by 1 substitutent selected from the group consisting of CMO alkyl, CM alkoxy, N(R10)R11, CN, F, CI, Br, I, CF 3 , (CH 2 ) m -
- RIO, Rl 1 , m, Yl and R50 as defined above, also with all their embodiments.
- Embodiments of the substituted ethene are propene, ethene- 1,1-diyldibenzene and 3,3-dimethylbut- 1-ene.
- An embodiment of the substituted ethine is 1-octyne.
- COMPSUBST is selected from a compound of formula (V) or a compound of formula (VI)
- R43 is H or CH 3 ;
- R44 is selected from the group consisting of Ci-io alkyl, C alkoxy, OH, N(R10)R11, CN, NO,
- RIO, Rl 1, m, Yl and R50 as defined above, also with all their embodiments.
- ALKHAL is a compound of formula (III);
- X is Br or I; preferably X is Br;
- R3 is Ci-20 alkyl or a Ci-20 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or CI, preferably by F;
- R3 is Ci-15 alkyl or Ci-15 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or CI, preferably by F;
- R3 is Ci-10 alkyl or Ci-10 alkyl wherein in the alkyl chain at least one hydrogen is substituted by F or CI, preferably by F.
- R3 is Ci-20 alkyl, more especially Ci-15 alkyl, even more especially Ci-10 alkyl, wherein all hydrogen atoms are independently substituted by CI or F,
- the alkyl is a linear perfluoro alkyl.
- X is Br or I
- X is I
- X is Br
- ALKHAL is a perfluoroalkyl halide, F2HC-CI or F2HC-Br, preferably
- ALKHAL is a perfluoroalkyl bromide or iodide, F2HC-CI or F2HC-Br;
- X is Br or I
- R3 is perfluoro Ci-20 alkyl, or
- ALKHAL is F 2 HC-C1 or F 2 HC-Br;
- X is Br or I
- R3 is perfluoro Ci-15 alkyl, or
- ALKHAL is F 2 HC-C1 or F 2 HC-Br;
- X is Br or I
- R3 is perfluoro Ci-10 alkyl, or
- ALKHAL is F2HC-CI or F 2 HC-Br.
- ALKHAL is selected from the group consisting of F21G0-I, FnCs-I, F13C6-I, F9C4-I, F3C-I, F 2 iCio-Br, FnCg-Br, Fi 3 C 6 -Br, F 9 C 4 -Br, F 3 C-Br, F3C-CI, F2HC-CI, and F 2 HC-Br; more in particular, ALKHAL is selected from the group consisting of n-F2iGo-I, n-FnCs-I, n- Fi 3 C 6 -I, n-F 9 C 4 -I, F3C-I, n-F 2 iCio-Br, n-F n C 8 -Br, n-Fi 3 C 6 -Br, n-F 9 C 4 -Br, F 3 C-Br, F3C-CI,
- ALKHAL is selected from the group consisting of F21C10-I,
- ALKHAL is selected from the group consisting of n-F2iGo-I, n-FnCs-I, n-Fi3C6-I, n-
- ALKHAL is selected from the group consisting of F2iGo-Br,
- reaction is performed in the presence of or using a catalyst CAT, CAT is Co-Ll/C, which is cobalt 1 ,10-phenanthroline supported on carbon,
- CAT is cobalt 1 ,10-phenanthroline supported on graphene.
- Co-Ll/C can be prepared according to SI. Catalyst preparation in the Supplementary Information of Westerhaus et al, Nature Chemistry, 2013, 5, 537-543, especially as described schematically in Figure 1 therein, that is by reacting Co(OAc)2 . 4 H 2 0 with 1 , 10-phenantroline and thereby forming a complex Co (phen)2(OAc) 2 which is then absorbed on carbon black and kept e.g. at 800 °C for 2 h under argon to provide Co-Ll/C, which contains cobalt oxide supported on 1,10- phenantroline/carbon black.
- the amount of Co in CAT is from 0.1 to 20 %, more preferably from 0.5 to 15 %, even more preferably from 1 to 12.5 %, especially from 2 to 12.5 %, the % are % by weight and are based on the total weight of CAT.
- the amount of Co in the reaction is from 0.001 to 20 %, more preferably from 0.01 to 15 %, even more preferably from 0.025 to 12.5%, especially from 0.05 to 10%, the % are % by weight % and are based on the weight of ALKHAL.
- the mol equivalents are based on the molar amount of ALKHAL.
- the reaction temperature of the reaction is preferably from 20 to 200°C, more preferably from 20 to 150°C, even more preferably from 40 to 150°C, especially from 70 to 150°C, more especially from 70 to 140°C, even more especially from 100 to 140°C.
- the reaction time of the reaction is preferably from 30 min to 72 h, more preferably from 6 h to 60 h, even more preferably from 10 h to 55 h.
- the reaction is done in the presence of a base BAS
- BAS is selected from the group consisting of Cs 2 C0 3 , CsHCOs, K2CO3, K3PO4, K2HPO4, KOAc, KOH, Mg(OH) 2 , TEA, DBU, and HNEt 2 .
- BAS is selected from the group consisting of CS2CO3, K2CO3, K3PO4, K2HPO4, KOAc, KOH, Mg(OH) 2 , TEA, DBU, and HNEt 2 .
- BAS is CS2CO3 or K2CO3;
- BAS is CS2CO3.
- the amount of BAS in the reaction is from 0.1 to 10 mol equivalents, more preferably 0.5 to 5 mol equivalents, even more preferably from 0.75 to 2.5 mol equivalents, the mol equivalents are based on the molar amount of ALKHAL.
- the reaction is done under inert atmosphere.
- the inert atmosphere is achieved by the use of an inert gas preferably selected from the group consisting of argon, another noble gas, lower boiling alkane, nitrogen and mixtures thereof.
- the lower boiling alkane is preferably a C 1-3 alkane, i.e. methane, ethane or propane.
- the reaction can be done in a closed system, or it can be done at a pressure caused by the chosen temperature in a closed system. It is also possible to apply pressure with said inert gas. It is also possible to carry out the reaction at ambient pressure.
- ALKHAL is a gaseous substance, e.g. in case of CF 3 Br
- ALKHAL can be used for applying the desired pressure, e.g. when charging ALKHAL.
- the reaction is done at a pressure of from 1 to 1000 bar, more preferably of from 1 to 500 bar, even more preferably of from 1 to 200 bar, especially of from 1 to 100 bar, more especially of from 1 to 50 bar.
- ALKHAL is a gaseous substance, e.g. in case of CF 3 Br
- pressure is applied, then preferably the reaction is done at a pressure of from 2 to 1000 bar, more preferably of from 2 to 500 bar, even more preferably of from 2 to 200 bar, especially of from 2 to 100 bar, more especially of from 2 to 50 bar.
- vapour pressure of CF 3 Br at ambient temperature is around 14 bar, so when CF 3 Br is used as ALKHAL, then preferably the reaction is done initially at a pressure of 14 bar or higher.
- the reaction can be done by using a solvent SOL.
- SOL is preferably selected from the group consisting of alkanes, chlorinated alkanes, ketones, ethers, esters, aliphatic nitrils, aliphatic amides, sulfoxides, and mixtures thereof.
- SOL is selected from the group consisting of C5-8 alkane, C5-C10 cycloalkane, chlorinated Ci-s alkane, acetone, methylethylketone (MEK), diethylketone, methyl tert-butyl ether (MTBE), tetrahydrofuran (THF), methyltetrahydrofuran, ethylacetate, butylacetate, valeronitril, acetonitrile, dimethylformamide (DMF), dimethylacetamide, N-methylpyrrolidone (NMP), dimethylsulfoxide (DMSO), dioxaneisopropanol, and mixtures thereof.
- MMF dimethylformamide
- NMP N-methylpyrrolidone
- DMSO dimethylsulfoxide
- SOL is selected from the group consitsing of acetone, MEK, heptane, cyclohexane, DMSO, dichloromethane, ethylacetate, dimethylacetamide, DMF, dioxane, THF, isopropanol, NMP, and mixtures thereof.
- SOL is acetone or methylethylketone;
- SOL is acetone
- COMPSUBST simultaneously as substrate and as solvent.
- reaction can also be carried out in the absence of a solvent, i.e. "in substance".
- a solvent i.e. "in substance”.
- COMPSUBST serves as solvent. This procedure is in particular applicable for compounds COMPSUBST being liquid at room temperature or having a low melting point of less than 40 °C.
- the amount of SOL is preferably from 0.1 to 100 fold, more preferably from 1 to 50 fold, even more preferably from 1 to 25 fold, especially from 1 to 15 fold of the weight of ALKHAL.
- ALKYLCOMPSUBST can be isolated by standard methods such as evaporation of volatile components, extraction, washing, drying, concentration, crystallization, chromatography and any combination thereof, which are known per se to the person skilled in the art.
- COMPSUBST, CAT, ALKHAL and BAS are commercially available and can be prepared according to known precedures.
- the reaction is done in the presence of a compound COMPSALT
- COMPSALT is selected from the group consisting of Nal, KJ, Csl, NaBr, KBr, CsBr,
- R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and Ci-io alkyl;
- R30, R31, R32 and R33 are identical or different and independently from each other selected from the group consisting of H and C2-6 alkyl;
- COMPSALT is selected from the group consisting of Nal, (n-Bu)4NI, NaBr, and
- the reaction is preferably done in the presence of a compound COMPSALT and X is Br.
- Conversion as used herein is calculated from the molar amount of the remaining ALKHAL( e.g. determining quantitative GC analysis with hexadecane as internal standard), in particular conversion denote the amount of ALKHAL which has reacted during the reaction.
- Selectivity denotes the molar amount of the desired product ALKYLCOMPSUBST based on reacted starting material.
- the gas atmosphere in the pyrex tube was flushed with nitrogen, the tube was closed with a screw cap and heated with stirring for the reaction time as stated, preferably for 24 h, at the reaction temperature as stated, preferably at 130°C.
- the resulting mixture was cooled to room temperature and diluted with dichloromethane, ether or methanol (10ml).
- the solids were removed by centrifugation (3000 rpm, 15 min) or by filtration.
- the obtained product solution was analyzed by quantitative GC analysis (internal standard hexadecane) or 19F-NMR analysis using the internal standards 1 ,2-difiuorobenzene or 1,4-difluorobenzene.
- Protocoll 3 General Procedure 3 "in substance" with ALKHAL which is gaseous at ambient temparture
- a mixture of the substrate COMPSUBST (1 eq, 2.5 mmol), Co-Ll/C (10 mol%, 0.25 mmol, 0.49 g, 3 wt% Co/C, prepared according to SI. Catalyst preparation in the Supplementary Information of Westerhaus et al., Nature Chemistry, 2013, 5, 537-543), and Cs 2 C0 3 (1.1 eq, 2.5 mmol, 0.894 g) was placed in a magnetically stirred Parr autoclave (Parr Instruments 4560 series). After replacing the air in the autoclave with nitrogen, ALKHAL gas was used to increase the pressure in the autoclave to 15 bars, the autoclave was sealed and heated at 130°C for 48 h with stirring.
- Protocoll 4 General Procedure 4 "in solution” with ALKHAL which is gaseous at ambient temparture
- ALKHAL gas was used to increase the pressure in the autoclave to 15 bars, the autoclave was sealed and heated at 130°C for 48 h with stirring. After cooling the reaction mixture to room temperature, the pressure was released from the autoclave, the reaction mixture diluted with 25 ml diethylether and 1 ,2-difluorobenzene (300 mg) was added as an internal standard. The solids were removed by centrifugation (3000 rpm, 15 min) or filtration. An aliquot was taken for quantitative GC-MS and 19 F-NMR analysis. The filtrate was concentrated under reduced pressure and the product isolated by column chromatography and gradient elution (1. pentane (100%, 10ml) 2. pentane : diethylether (1 : 1 v/v, 10 ml)) to give the product ALKYLCOMPSUBST.
- ALKHAL has a linear chain, if not otherwise stated.
- CS means COMPSUBST.
- AH means ALKHAL.
- IS means isomer(s).
- Reactuion time was 16 h, except for entry 6, where the reaction time was 20 h.
- BAS was Cs 2 C0 3 .
- CAT was 5 wt% Co-Ll/C.
- Any alkyl chain is a linear alkyl chain, if not otherwise stated.
Abstract
Description
Claims
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CN201880049832.9A CN110944965A (en) | 2017-07-28 | 2018-07-26 | Method for the heterogeneously cobalt-catalyzed production of alkylated or fluoroalkylated, chloroalkylated, and fluorochloroalkylated compounds |
JP2020504193A JP7219752B2 (en) | 2017-07-28 | 2018-07-26 | Process for the preparation of heterogeneous cobalt catalyzed alkylation or fluoro, chloro and fluorochloro alkylated compounds |
US16/632,572 US10968187B2 (en) | 2017-07-28 | 2018-07-26 | Method for preparation of alkylated or fluoro, chloro and fluorochloro alkylated compounds by heterogeneous cobalt catalysis |
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