JP5013071B2 - Method for producing aromatic compound using iron catalyst - Google Patents

Description

  The present invention relates to a liquid crystal compound and a method for producing an aromatic compound useful mainly as a raw material for synthesizing a liquid crystal compound by using an iron salt as a catalyst.

In recent years, with the widespread use of mobile phones and the like, liquid crystal display elements with low power consumption, light weight, and good display characteristics have attracted attention.
In the liquid crystal display element, the classification based on the operation mode of the liquid crystal includes PC (phase change), TN (twisted nematic), STN (super twisted nematic), BTN (Bistable twisted nematic), ECB (electrically controlled birefringence), OCB ( optically compensated bend), IPS (in-plane switching), VA (vertical alignment), and the like. The classification based on the element driving method is PM (passive matrix) and AM (active matrix). PM (passive matrix) is classified into static and multiplex, and AM is classified into TFT (thin film transistor) and MIM (metal insulator metal).

  These devices contain a composition having appropriate physical properties. In order to improve the characteristics of the device, the composition preferably has appropriate physical properties. The general physical properties necessary for the compound that is a component of the composition are as follows. (1) Chemical stability and physical stability. (2) High clearing point. The clearing point is a liquid crystal phase-isotropic phase transition temperature. (3) Low minimum temperature of the liquid crystal phase. The liquid crystal phase means a nematic phase, a smectic phase, or the like. (4) Small viscosity. (5) Appropriate optical anisotropy. (6) Appropriate dielectric anisotropy. A compound having a large dielectric anisotropy often has a large viscosity. (7) Large specific resistance.

  The liquid crystal composition used in the device is preferably a compound having a good liquid crystal display temperature range that can cover the use temperature range. As a liquid crystal compound having a wide liquid crystal temperature range, several 6-membered ring structures connected in series are good in that they can simultaneously achieve physical, chemical stability and required liquid crystal properties. It is used as a component of a liquid crystal composition used in a display element. On the other hand, since around 1995, compounds having a halogenated phenyl group such as fluorobenzene and chlorobenzene have been frequently used. This is characterized by good characteristics as a component of a TN liquid crystal display element in which the cyclohexyl (ethyl) benzene structure as the mother skeleton is currently used, that is, a wide liquid crystal phase temperature range and low viscosity. This is because the. Further, these skeletal compounds mainly have an optical anisotropy value that can easily achieve the retardation used, and have a large elastic constant ratio that enables a high-speed response.

Furthermore, recently, compounds having alkenyl at the molecular end, such as cyclohexyl (ethyl) benzene having an alkenyl group at the end, have good compatibility and low viscosity in TFT liquid crystal compositions for color monitors. It has come to be used frequently because it has the advantage of not lowering the point.

  As a method for producing these compounds having a cyclohexyl (ethyl) benzene skeleton, a benzyl alcohol derivative obtained by reacting the corresponding cyclohexanone or cyclohexylacetaldehyde and an aryl Grignard reagent is dehydrated to obtain a cyclohexene derivative or a cyclohexyl vinyl derivative. Hydrogenation methods are used industrially. This method is extremely disadvantageous when using substrates having substituents that are decomposed by hydrogenation or converted to other functional groups. That is, when a Grignard reagent prepared from chlorobromobenzene or cyclohexanenone having an alkenyl at the molecular end is used, the desired product cannot be obtained directly, so a protective group must be used.

  On the other hand, a catalytic method for synthesizing cyclohexylbenzene or cyclohexylethylbenzene by directly reacting a cyclohexane ring and a benzene ring or a cyclohexylethyl group with a benzene ring has not reached a practical level.

Conventionally, as a regioselective synthesis method of an aromatic compound having an alkyl group, a method of coupling an alkyl organometallic reagent with a halogen aryl or aryl sulfonate in the presence of a nickel or palladium catalyst is known. . (Hayashi, T .; Konishi, M .; Kobori, Y.,; Kumada, M .; Higuchi, T .; Hirotsu, K., J. Am. Chem. Soc. 1984, 106, 158-163, Ogasawara, M. ; Yoshida, K.,; Hayashi, T. Organometallics, 2000, 19, 1567-1571, Doherty, S .; Knight, J .; Robins, EG; Scanlan, TH; Champkin, PAClegg, WJAm Soc. 2001, 123, 5110-5111).
However, according to this method, it is essential to add a phosphine ligand having a complicated structure, and depending on the structure of the secondary alkyl group, there is isomerization from the secondary alkyl group to the primary alkyl group, There was a problem that the target product could not be obtained in high yield. In addition, there is a problem that a highly toxic or expensive catalyst such as a nickel catalyst or a palladium catalyst is necessary, and there is a problem that it cannot be applied to mass synthesis.

In addition, as a method for producing an aromatic compound having an alkyl group from an alkyl halide or an alkyl sulfonate ester and an aromatic organometallic reagent, an alkyl halide or an alkyl sulfonate ester and an aromatic compound using a diene ligand or palladium as a catalyst Method of cross-coupling magnesium reagent (Terao, J .; Naitoh, Y .; Kuniyasu, H .; Kambe, N. Chem Lett. 200332, 890-891) and copper and nickel in the presence of diene ligand Catalytic cross-coupling of alkyl halides and aromatic magnesium reagents (Terao, J .; Ikumi, A .; Kuniyasu, H .; Kambe, NJAm. Chem. Soc. 2003, 125 5649-5647)
Is also known.

In addition, in the presence of bulky phosphine ligands such as tricyclohexylphosphine, catalytic coupling reactions of alkyl halides with aromatic zinc compounds, aromatic tin compounds or aromatic silicon compounds (Zhou, J .; Fu, GCJAm.Chem. Soc. 2003,125,12527-12530, Tang, H .; Menzel, K .; Fu, GC Angew. Chem., Int. Ed. 2003,42-5079-5082, Lee, J.-Y .; Fu, GCJAm. Chem. Soc. 2003, 125, 5616-5617) is also known.
However, when a secondary alkyl group is introduced by these methods, an alkene is generated by a side reaction such as elimination reaction, and the target compound is purified only in a low yield. Therefore, an aromatic compound having a secondary alkyl substituent is used. There was a problem that it could not be applied to the synthesis of.
In addition, as a method of producing an aromatic compound having an alkyl group from a secondary alkyl halide and an aromatic organometallic compound, an aromatic boron compound using a nickel catalyst is catalytically cross-coupled with a secondary alkyl halide. A reaction method is also known, Zhou, J .; Fu, GCJ Am. Chem. Soc. 2004, 126, 1340-1341). According to this method, aromatic compounds having various secondary alkyl substituents can be synthesized, but problems such as having to use a highly toxic nickel catalyst have not been solved.

Further, as a method using an inexpensive and low-toxic iron catalyst as a catalyst, an electrophile such as an unsaturated organic halide such as aryl halide or alkenyl halide or allyl phosphate ester, and an aromatic or alkylmagnesium reagent A method of cross-coupling reaction with a zinc reagent or a manganese reagent is known. (Furstner, A .; Leiter, A. Angew. Chem., Int. Ed. 2002,41,609-612, Furstner, A .; Leiter, A .; Mendez, M .; Krause, HJAm.Chem.Soc. 2002, 124,13856-13863, US 2003/0220498).
By this method, it is possible to synthesize an aromatic compound having a secondary alkyl substituent from a secondary alkylmagnesium reagent and an aryl halide. However, in addition to the fact that many functional groups such as a carbonyl group and a cyano group cannot coexist when preparing the secondary alkyl magnesium reagent, the yield is as low as 50 to 60%, which is not a general-purpose method. When an alkyl halide and an aromatic magnesium reagent are used under the reaction conditions, there is a problem that the production of the olefin is given priority due to side reactions such as elimination reaction, and the target product is produced only in a low yield.

  Also known is a method of performing a coupling reaction between an alkyl halide and an aromatic magnesium reagent using an iron complex catalyst having a catalytic amount of N, N, N ′, N′-tetramethylethylenediamine (TMEDA) as a ligand. (Martin, R .; Furstner, AA Angew. Chem., Int. Ed. 2004, 43, 3955-3957) However, according to this method, when chlorides and fluorides are used as alkyl halides, Had the problem that the reaction did not proceed at all.

Further, a method of performing a coupling reaction in the same manner as described above, except that trivalent iron acetylacetonate and a complex are used as a catalyst and the solvent is changed from tetrahydrofuran (THF) to diethyl ether without using a diamine ligand. Is also known. (Nagano, T .; Hayashi, T. Org. Lett. 2004, 6, 1297-1299). However, this method also has a problem that the reaction does not proceed at all when chloride or fluoride is used as the alkyl halide. In addition, the yield is generally low, which is not a practical method.
For this reason, there has been a demand for a method for obtaining a large variety of aromatic compounds such as cyclohexylbenzene and cyclohexylethylbenzene in a high yield by a highly safe method capable of mass synthesis.

Conventional manufacturing methods are disclosed in the following documents.
Angew. Chem., Int. Ed. 2004, 43, 3955-3957 Org. Lett. 2004, 6, 1297-1299

  An object of the present invention is to provide a process for producing an aromatic compound that is useful as a liquid crystal compound or a synthesis intermediate of a liquid crystal compound, which eliminates the problems of the conventional techniques described above, can be purified, and has a high conversion rate. is there.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by using a diamine compound and an iron catalyst, from a compound having a leaving group represented by the following formula I and an organometallic compound represented by the following formula II, The present invention was completed by finding a method for easily producing an aromatic compound represented by the following formula III in a selective and high yield. Further, the product obtained by the production method of the present invention can be easily isolated and purified by an operation such as distillation which is usually used industrially.

  The advantage of the present invention is that it is a method for producing a liquid crystal compound or an aromatic compound useful as a synthesis intermediate of a liquid crystal compound, which can be purified and has a high conversion rate. By using the production method of the present invention, a liquid crystal compound or an aromatic compound useful as a raw material for synthesizing a liquid crystal compound can be easily produced with high selectivity and high yield. This method is also superior in that there are few by-products as compared to the commonly used method.

  That is, the present invention provides the production of an aromatic compound represented by the formula III, which comprises reacting a compound represented by the formula I and a compound represented by the formula II in the presence of a diamine and an iron salt catalyst. Is the method.

The present invention includes the following items.
[1] A process for producing an aromatic compound represented by formula III, comprising reacting two compounds of a compound represented by formula I and a compound represented by formula II in the presence of a diamine compound and an iron catalyst.

Wherein ring A is independently 1,4-phenylene, 1,4-phenylene in which one or more —H is replaced with —F, and one or more —CH═ is replaced with —N═. 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexylene in which one or two discontinuous —CH ₂ — is replaced by —O— or —S—, or 1,4-cyclohexyl R ¹ is —H or alkyl having 1 to 15 carbons, and one or two or more consecutive —CH ₂ — in the alkyl is —O—, —S— or —CH═. One or more —H in the alkyl may be replaced by —F; Z is independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O; _{-, - OCH 2 -, -} COO -, - OCO -, - CF 2 O _{, -OCF 2 -, - CH =} CH-, or a -C≡C-; X is an arylsulfonyloxy, alkylsulfonyloxy alkylsulfonyloxy or one or more -H is replaced with -F; n is an integer from 0 to 3 and m is 0 or 2;
M is Li, MgBr, MgCl, ZnBr, ZnCl, SnCl, or SnBr; L ¹ , L ^2, and L ³ are independently —H or —F; R ² is —H, halogen, carbon number 1 ˜15 alkyl, or a group of formula IIa, wherein one or two or more consecutive —CH ₂ — in the alkyl is replaced by —O—, —S— or —CH═CH—. One or more -H in the alkyl may be replaced by -F. )

（式中、Ｇは単結合、−ＣＨ_２ＣＨ_２−、−ＣＨ_２Ｏ−または−ＯＣＨ_２−であり；Ｌ^４およびＬ^５は独立して−Ｈまたは−Ｆであり；Ｒ^３は−Ｈ、ハロゲン、または炭素数１〜１５のアルキルであり、このアルキル中の一つまたは連続しない二つ以上の−ＣＨ_２−は−Ｏ−、−Ｓ−または−ＣＨ＝ＣＨ−で置き換えられてもよく、またこのアルキル中の一つ以上の−Ｈは−Ｆで置き換えられてもよい。）

Wherein G is a single bond, —CH ₂ CH ₂ —, —CH ₂ O— or —OCH ₂ —; L ⁴ and L ⁵ are independently —H or —F; R ³ is — H, halogen, or alkyl having 1 to 15 carbon atoms, wherein one or two or more consecutive —CH ₂ — in the alkyl are replaced by —O—, —S— or —CH═CH—. And one or more -H in the alkyl may be replaced by -F.)

[2] In formula I, ring A is independently monofluoro-1,4-phenylene, difluoro-1,4-phenylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5. - diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, be a 1,3-dioxane-2,5-diyl or tetrahydropyran-2,5-diyl,; ^{R 1} is -H, carbon atoms 1 to 15 alkyl, C 1 to C 14 alkoxy, or C 1 to C 16 alkenyl; Z is independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —. , -CH = CH-, or -C≡C-; n is an integer from 0 to 2;
In Formula II, L ¹ , L ² and L ³ are independently H or F; R ² is —H, —F, C 1-15 alkyl, C 1-14 alkoxy, or C 1-16 alkenyl, or a group of formula IIa;
In Formula IIa, R ³ is —H, —F, C 1-15 alkyl, C 1-14 alkoxy, or C 1-16 alkenyl.
The manufacturing method of the aromatic compound of item [1].

[3] In the formula I, ring A is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; R ¹ is —H, carbon number 1 ˜15 alkyl, or alkenyl having 1 to 16 carbon atoms; Z is independently a single bond or —CH ₂ CH ₂ —; n is 0 or 1;
In Formula II, M is Li, MgBr, MgCl, ZnBr, or ZnCl; R ² is —H, —F, C 1-15 alkyl, C 1-14 alkoxy, or C 1-16 Or a group of formula IIa;
In Formula IIa, R ³ is —H, —F, C 1-15 alkyl, C 1-14 alkoxy, or C 1-16 alkenyl.
The manufacturing method of the aromatic compound of item [1].

[4] The method for producing an aromatic compound according to any one of items [1] to [3], wherein in formula I, X is methanesulfonyloxy, paratoluenesulfonyloxy, or trifluoromethanesulfonyloxy.

[5] The method for producing an aromatic compound according to any one of items [1] to [4], wherein the iron catalyst is an iron salt or an iron complex.

[6] The method for producing an aromatic compound according to any one of items [1] to [4], wherein the iron catalyst is an iron salt.

[7] Any of items [1] to [6], wherein the diamine compound is one or more selected from tetraalkylethylenediamine, tetraalkylpropylenediamine, a metal salt complex of tetraalkylethylenediamine, and a metal salt complex of tetraalkylpropylenediamine. A process for producing the aromatic compound according to claim 1.

[8] The method for producing an aromatic compound according to any one of items [1] to [6], wherein the diamine compound is tetramethylethylenediamine and / or a metal salt complex thereof.

[9] The method for producing an aromatic compound according to any one of items [1] to [6], wherein the diamine compound is a metal salt complex of tetramethylethylenediamine.

R ¹ in Formula I, R ² in Formula II, and R ³ in Formula IIa are —H, halogen, or alkyl having 1 to 15 carbons, and one or two or more non-continuous —CH in the alkyl. _2- may be replaced with -O-, -S- or -CH = CH-, and one or more -H in the alkyl may be replaced with -F. Examples of the alkyl of R ¹ , R ² and R ³ include linear alkyl such as methyl, ethyl, n-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl and pentadecyl, And branched alkyl such as 2-methylbutyl, 2-octyl, and 3,3-dimethylnonyl.

Examples of alkyl in which one or two or more consecutive —CH ₂ — may be replaced by —CH═CH— and —O— include alkenyloxy such as 2-propenyloxy and 2-butenyloxy, and vinyl. And alkenyloxyalkyl such as oxymethyl and 3-butenyloxymethyl. Examples of alkyl where one or more -H may be replaced by -F include fluoromethyl, difluoromethyl, trifluoromethyl, 1,1,2-trifluoroethyl, 2,2-difluoroethyl, pentafluoro And fluoroalkyl such as ethyl, 1,2,2-trifluoropropyl, 4,4,6,6-tetrafluorobutyl and 3,3,4,4,5,5,6,6-octafluorooctyl. .

Examples of alkyl in which one or more —H is replaced by —F and one or two or more consecutive —CH ₂ — may be replaced by —O— include trifluoromethoxy, 2, Examples include fluoroalkoxy such as 2-difluoroethoxy, pentafluoroethoxy, 2,2,3,3,3-pentafluoropropyloxy and perfluorohexyloxy. Examples of alkyl in which one or more —H may be replaced with —F and one or two or more consecutive —CH ₂ — may be replaced with —CH═CH— include 2,2- And fluoroalkenyl such as difluorovinyl, 3,3-difluoro-2-propenyl and 4,4-difluoro-3-butenyl.
Halogen includes fluorine, chlorine and bromine.

  X in formula I is halogen, arylsulfonyloxy, alkylsulfonyloxy or alkylsulfonyloxy in which one or more —H is replaced by —F. Examples of X being arylsulfonyloxy include benzenesulfonyloxy and paratoluenesulfonyloxy. Examples of alkylsulfonyloxy include methanesulfonyloxy. Examples of alkylsulfonyloxy in which one or more —H is replaced by —F include fluoromethanesulfonyloxy, difluoromethanesulfonyloxy, trifluoromethanesulfonyloxy, fluoroethanesulfonyloxy, trifluoroethanesulfonyloxy, perfluoroethane And sulfonyloxy.

  Ring A includes 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene, and 1,4-cyclo Examples include xylene, 1,4-cyclohexylenylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl and the like.

  The iron catalyst used in the present invention is preferably a divalent or trivalent catalyst. Divalent iron salts include iron (II) acetate, iron (II) bromide, iron (II) chloride, iron (II) iodide, iron (II) fluoride, iron (II) oxalate, iron phthalocyanine (II), iron sulfate (II), iron sulfide (II), etc. are preferred, and trivalent iron salts include iron, iron acetate (III), iron bromide (III), iron chloride (III), and iodide. Iron (III), iron fluoride (III), iron oxalate (III), iron phthalocyanine (III), iron sulfate (III), iron sulfide (III), iron nitrate (III) and the like are preferable.

When the iron catalyst is an iron complex, the ligand is preferably carbonyl, halogen atom, Schiff base, polyamine, dimethylformamide or the like. Specific examples of these iron complexes include monovalent carbonyl iron complexes [FeCp (CO) ₂ ] ₂ , divalent neutral Schiff base complexes (2,6-Bis [1- (2,6-dialkylmethylphenylimino) ethyl] pyridine iron (II) chloride), a trivalent cationic tetramine complex, a trivalent dimethylformamide complex, or the like can be used. The iron catalyst of the present invention is preferably an iron salt from the viewpoint of easy handling and availability, and FeCl ₃ is particularly preferable. In the method for producing an aromatic compound according to the present invention, an amine compound can be used as an additive. By adding an amine compound in the present invention, generation of by-products can be reduced.

  As the amine compound to be used, a trisubstituted amine compound, a diamine compound, or the like is used, but it is particularly preferable that it can be used as a bidentate ligand, in particular, N, N, N ′, N′-tetramethylethylenediamine, A compound having two amino groups in one molecule such as N, N, N ′, N′-tetramethylpropylenediamine is more preferable.

  In the present invention, the amount of the amine compound is preferably in the range of 0.5 equivalent to 10 equivalents relative to 1 mol of the compound represented by the above formula II, in terms of good yield, more preferably 1 to 1 equivalent. It is in the range of 3 equivalents, and more preferably in the range of 1 to 2 equivalents.

In the present invention, the amine compound may be a complex with an appropriate metal salt, and the metal salt used may be a halogenated transition metal or a typical halogenated element, preferably a halogenated Examples thereof include metal salts selected from zinc, copper halide, magnesium halide, nickel halide and the like. Further, among these metal salts, it is preferable to use a compound which is iodine as a halogen, and zinc iodide is particularly preferable. The amount of these metal salts used is preferably in the range of 0.5 to 3 equivalents relative to the diamine, and more preferably about 1 equivalent in terms of not inhibiting the reaction.
These metal salts can be mixed with a diamine compound in advance to be complexed.

  In the present invention, typically, an aromatic organometallic compound represented by the formula II and the above-described amine compound or a mixture of an amine compound and a metal salt are added to a solution having the compound represented by the formula I and an iron catalyst and stirred. To do. Alternatively, the aromatic organometallic compound represented by the formula II is added to the solution having the compound represented by the formula I, the iron catalyst, and the amine compound and stirred.

  These iron catalysts can also be carried out in the presence of a Lewis acid such as titanium tetrachloride or boron trifluoride diethyl ether complex. In this case, the addition amount of Lewis acid is preferably in the range of 0.1 to 200 mol% with respect to the iron salt, and more preferably in the range of 3 to 10 mol% with respect to the iron salt in terms of good reaction yield. preferable.

  These iron catalysts may be used by mixing with lithium salts such as lithium chloride, lithium bromide and lithium iodide. In this case, the addition amount of the lithium salt is preferably in the range of 10 to 200 mol% with respect to the iron salt, and more preferably about equimolar (100 mol%) with respect to the iron salt in terms of good reaction yield.

  The addition amount of the iron catalyst used in the present invention is not particularly limited as long as the effect of the present invention is not hindered, but is preferably in the range of 0.5 to 200 mol% with respect to the compound represented by the formula I. More preferably, it is the range of 1-100 mol%, More preferably, it is the range of 5-50 mol%, Most preferably, it is the range of 10-30 mol%.

  The reaction solvent used in the production method of the present invention may be any one that does not inhibit the reaction itself. Hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as toluene and benzene, ether solvents such as diethyl ether, tetrahydrofuran, dioxane and tertiary butyl methyl ether, and dimethylformamide and N-methylpyrrolidinone These can be selected from general solvents such as amides, and can be used alone or as a mixture of a plurality of solvents. In particular, it is preferable to use the solvent used in preparing the organometallic reagent of the formula II as it is because the operation is simple.

  It is desirable that the reaction of the present invention is carried out under appropriate reaction temperature conditions. That is, it is preferably performed between −78 ° C. and the boiling point of the solvent used from the viewpoint of simplifying the operation. In consideration of the balance between the reaction rate and the amount of by-products generated, it is more preferable that the reaction is carried out between -20 ° C and 50 ° C. Although the reaction of the present invention can be carried out in the air, it is preferably carried out in an inert gas atmosphere such as nitrogen and argon.

  In any case, from the viewpoint of increasing the yield, the addition is preferably carried out slowly. Although the rate of dropping depends on the scale of the reaction, for example, when the amount of the compound represented by formula I is about 50 mmol, the solution of the aromatic organometallic compound formula II is added at a rate of about 1 mmol / min. It is preferable from the viewpoint of improving the conversion rate. When the amount of the compound represented by formula I is about 1 mmol, it is preferable to add the aromatic organometallic compound and the solution of formula II at about 0.06 mmol / min.

  In the production method of the present invention, the product can be isolated from the reaction system after completion of the reaction by a method used in ordinary chemical operation. For example, water can be added to the reaction solution to deactivate the unreacted organometallic reagent represented by Formula II, and then extracted from the reaction system with an organic solvent. The reaction product can be brought into a higher purity state by performing purification operations such as recrystallization, distillation, silica gel chromatography or the like alone or in combination as necessary. Alternatively, the desired compound can be obtained by converting the functional group without purifying the reaction product, converting the functional group to a compound that is easier to purify, and then performing the above-described purification operation alone or in combination.

  The compound of the formula I which is a raw material of the present invention is a generally known and simple method described in the fourth edition, experimental chemistry course (edited by the Chemical Society of Japan, Maruzen Publishing Co., Ltd.) from the corresponding alcohol derivative. It can be synthesized by the method. That is, a compound in which X is sulfonyloxy is obtained by reacting an alcohol represented by the formula I (X = OH) with a substituted sulfonyl chloride or sulfonic anhydride in the presence of an amine base such as triethylamine, diethylamine, pyridine and dimethylaminopyridine. Is synthesized in a high yield.

  The organometallic compounds of formula I and formula II, which are the raw materials of the present invention, are prepared by reacting the corresponding halide of formula II (M = halogen) with metal magnesium, metal lithium, etc. based on general techniques. The Alternatively, it is prepared by treating these halides with a solution such as alkyl lithium. It is also prepared by converting the prepared organometallic compound into a different metal by a metal exchange reaction. The reagent of formula II is preferably used in the next reaction as it is without being isolated after preparation in terms of simplifying the operation. Therefore, the reagent of formula II is preferably prepared using a solvent that does not inhibit the synthesis reaction of the aromatic compound. That is, hydrocarbons such as pentane, hexane, heptane and octane, aromatic hydrocarbons such as toluene and benzene, ether solvents such as diethyl ether, tetrahydrofuran, dioxane and tertiary butyl methyl ether, and dimethylformamide and N-methylpyrrolidinone It is preferable to prepare a reagent of formula II by selecting from general solvents such as amides, etc., alone or in combination with a plurality of solvents.

  EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The NMR spectra of the products described in the examples showed the value of δ obtained by measuring Mercury VX300 MHz manufactured by Varian and using TMS as an internal standard.

[Example 1]
4 ′-(4-Fluorophenyl) -4-pentylbicyclohexyl (in formula III, R ¹ = n—C ₅ H ₁₁ , ring A = cyclohexylene, Z = single bond, L ₁ = L ₂ = L ₃ = H, R ₂ = F, n = 1, and m = 0)

  Zinc iodide-tetramethylethylenediamine complex (326 mg, 0.75 mmol) and lithium iodide (100 mg, 0.75 mmol) were added to p-fluorophenylmagnesium bromide (1.03 M, THF solution, 1.46 ml, 1.50 mmol). In addition, the mixture was stirred at 0 ° C. for 20 minutes. 4- (4-Pentylcyclohexyl) cyclohexyl p-toluenesulfonate (203 mg, 0.5 mmol) was added to the resulting suspension, and iron (II) chloride (0.1 M, THF solution, 0.25 ml, 0.025 mmol) was added. ) Was added dropwise at 0 ° C. The reaction mixture was stirred at 25 ° C. for 48 hours, and further stirred at 40 ° C. for 12 hours. After completion of the reaction, the solution was quenched with saturated ammonium chloride, the mixture was filtered through a Florisil pad and concentrated under reduced pressure, and the resulting product was isolated and purified using silica gel column chromatography to give the title compound ( 96 mg, yield 58%, trans / cis = 64/36).

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.25-7.10 (m, 2H), 7.03-6.90 (m, 2H), 2.62 (quint, J = 6.9 Hz, 0.36H), 2.42 (tt, J = 12.3 Hz, 3.0 Hz, 0.64H), 2.05-0.75 (m, 30H) .;
¹³ C-NMR (75.5 MHz) δ 161.2 (d, J = 243 Hz, trans-isomer), 161.1 (d, J = 243 Hz, cis-isomer), 143.5 (d, J = 2.9 Hz, trans-isomer) , 143.0 (d, J = 3.2 Hz, cis-isomer), 128.3 (d, J = 7.5 Hz, 2C, cis-isomer), 128.0 (d, J = 7.8 Hz, 2C, trans-isomer), 114.9 (d , J = 20.9 Hz, 2C, trans-isomer), 114.8 (d, J = 20.9 Hz, 2C, cis-isomer), 44.2 (s), 43.7 (s), 43.2 (s), 42.3 (s), 39.7 (s), 38.2 (s), 38.0 (s), 37.7 (s), 37.6 (s), 37.4 (s), 35.0 (s), 33.9 (s), 33.8 (s), 32.5 (s), 31.2 (s), 30.6 (s), 30.4 (s), 29.8 (s), 27.7 (s), 26.9 (s), 26.8 (s).

  Similar to this example, the following compounds can also be synthesized.

  By using the production method of the present invention, a liquid crystal compound or an aromatic compound useful as a raw material for synthesizing a liquid crystal compound can be easily produced with high selectivity and high yield. This method has fewer by-products than the commonly used methods.

Claims (8)

A process for producing an aromatic compound represented by formula III, comprising reacting two compounds of a compound represented by formula I and a compound represented by formula II in the presence of a diamine compound and an iron catalyst. Here, the diamine compound is a tetraalkylethylenediamine and / or a metal salt complex of tetraalkylethylenediamine.

Wherein ring A is independently 1,4-phenylene, 1,4-phenylene in which one or more —H is replaced with —F, and one or more —CH═ is replaced with —N═. 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexylene in which one or two discontinuous —CH ₂ — is replaced by —O— or —S—, or 1,4-cyclohexyl R ¹ is —H or alkyl having 1 to 15 carbons, and one or two or more consecutive —CH ₂ — in the alkyl is —O—, —S— or —CH═. One or more —H in the alkyl may be replaced by —F; Z is independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O; _{-, - OCH 2 -, -} COO -, - OCO -, - CF 2 O _{, -OCF 2 -, - CH =} CH-, or a -C≡C-; X is an arylsulfonyloxy, alkylsulfonyloxy alkylsulfonyloxy or one or more -H is replaced with -F; n is an integer from 0 to 3 and m is 0 ;
M is Li, MgBr, MgCl, ZnBr, ZnCl, SnCl, or SnBr; L ¹ , L ^2, and L ³ are independently —H or —F; R ² is —H, halogen, carbon number 1 ˜15 , wherein one or two or more consecutive —CH ₂ — in the alkyl may be replaced by —O—, —S— or —CH═CH—, and One or more -H may be replaced by -F. ) In formula I, ring A is independently monofluoro-1,4-phenylene, difluoro-1,4-phenylene, 1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; R ¹ is —H and has 1 to 15 carbon atoms Alkyl, C 1-14 alkoxy, or C 1-16 alkenyl; Z is independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —CH = CH-, or -C≡C-; n is an integer of 0-2;
In Formula II, L ¹ , L ² and L ³ are independently H or F; R ² is —H, —F, C 1-15 alkyl, C 1-14 alkoxy, or C 1 to 16 of alkenyl,
The manufacturing method of the aromatic compound of Claim 1. In Formula I, Ring A is 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or tetrahydropyran-2,5-diyl; R ¹ is —H and has 1 to 15 carbon atoms Alkyl or alkenyl having 1 to 16 carbon atoms; Z is independently a single bond or —CH ₂ CH ₂ —; n is 0 or 1;
In Formula II, M is Li, MgBr, MgCl, ZnBr, or ZnCl; R ² is —H, —F, C 1-15 alkyl, C 1-14 alkoxy, or C 1-16 Alkenyl of
The manufacturing method of the aromatic compound of Claim 1.   The method for producing an aromatic compound according to any one of claims 1 to 3, wherein in the formula I, X is methanesulfonyloxy, paratoluenesulfonyloxy, or trifluoromethanesulfonyloxy.   The method for producing an aromatic compound according to any one of claims 1 to 4, wherein the iron catalyst is an iron salt or an iron complex.   The method for producing an aromatic compound according to any one of claims 1 to 4, wherein the iron catalyst is an iron salt.   The method for producing an aromatic compound according to any one of claims 1 to 6, wherein the diamine compound is tetramethylethylenediamine and / or a metal salt complex thereof.   The method for producing an aromatic compound according to any one of claims 1 to 6, wherein the diamine compound is a metal salt complex of tetramethylethylenediamine.