JP2003509507A - Liquid crystal compound - Google Patents

Abstract

(57) [Summary] A liquid crystal compound represented by the following general formula (I): In the formula, X is O, S or Se, and R ¹ , R ² , R ³ , R ⁴ , m, n, p and q are liquid crystal compounds specified in the present application. A liquid crystal device comprising the compound is also claimed.

Description

Detailed Description of the Invention

The present invention relates to novel compounds having joined heterocyclic rings with the properties of liquid crystals,
The present invention also relates to a method for preparing them and a liquid crystal device incorporating them. The term "liquid crystal" is well known. It means compounds which, as a result of their structure, orient themselves in the same direction, preferably at working temperatures, eg -40 to 200 ° C. These materials are useful in a variety of devices, especially liquid crystal display devices or LCDs. Liquid crystals can exist in different phases. In essence, there are three different types of liquid crystal materials, each with a characteristic molecular arrangement. These types are nematic, chiral nematic (cholesteric) and smectic. In general, molecules of nematic compounds align molecules in a bulk material with a unique orientation. Smectic materials are similarly oriented and closely align the molecules within the layers.

There are a wide range of smectic phases, such as smectic A and smectic C. In the former, the molecules can be aligned perpendicular to the base or support, in the latter the molecules can be tilted with respect to the support. Some liquid crystal substances have many liquid crystal phases in response to temperature changes. Others have only a single phase. For example, the liquid crystal material may exhibit the following phases when cooled: -Isotropic-Nematic-Smectic A-Smectic C.
-Solid. When a substance is described as Smectic A, it means that the substance has a Smectic A phase over the working temperature range. Such materials are particularly useful in display devices, where the ability to align and rearrange them under the influence of voltage is used to affect the path of polarization resulting in liquid crystal displays. They are widely used in devices such as things to see, calculators, display boards or stores, computer screens, especially laptop computer screens and the like. The characteristics of the compound, which affect the speed when the compound responds to the voltage charge, include molecular size, viscosity (Δn), polar moment (Δε), and conductivity.

Some examples of bicyclic liquid crystal compounds can be found in DE-A-19900517 and WO98 / 04544. Applicants have discovered a new class of compounds with useful liquid crystal properties. In particular, the invention provides a liquid crystal compound having a joined 5- and 6-membered ring, at least one of said rings containing a heteroatom, and at least one of said rings having a substituent. Preferably, each ring has at least one substituent. Suitable heteroatoms for the ring system of the present invention include oxygen, sulfur, nitrogen and selenium. The nitrogen, if present, may carry hydrogen or substituents, depending on the nature and aromaticity of the ring system. The ring system may be aromatic or non-aromatic, but is preferably aromatic. Specific examples of ring systems of the present invention include benzofuran and benzopyran.

The nature of the substituents on the ring determines the unique liquid crystal properties of the compound. Larger substituents tend to increase the viscosity of the compound, thereby increasing the time for the molecule to adopt the proper orientation under the influence of voltage. The number of free electrons contained within the substituent affects the optical properties of the compound. Aromatic rings have relatively high conductivity, while strong electronegative groups such as cyano tend to reduce conductivity. Thus, the nature of the substituents on the ring can be selected to give the final compound the desired liquid crystal properties. For example, some applications described below require chiral molecules. For this purpose, the compounds according to the invention preferably contain asymmetric centers. Typical substituents include functional groups, optionally substituted hydrocarbyls, optionally substituted alkoxys, optionally substituted heterocycles or carboxys or hydrocarbyl esters or amides thereof.

As used herein, the term “hydrocarbyl” means any structure containing carbon and hydrogen atoms. It may be, for example, alkyl, alkenyl, alkynyl, aryl such as phenyl or naphthyl, arylalkyl, cycloalkyl, cycloalkenyl or cycloalkynyl. Suitably they contain up to 20, preferably up to 10 carbon atoms. The term "heterocycle" includes, for example, 4 to
Included are aromatic or non-aromatic rings containing 20 and preferably 5 to 10 ring atoms, at least one of which is a heteroatom such as oxygen, sulfur or nitrogen. Examples of such groups include furyl, thienyl, pyrrolyl, pyrrolidinyl, imidazolyl, triazolyl, thiazolyl, tetrazolyl, oxazolyl, isoxazolyl,
Mention may be made of pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, benzthiazolyl, benzoxazolyl, benzothienyl or benzofuryl.

As used herein, the term “alkyl” is suitably 20 and preferably 6
Refers to a straight or branched chain alkyl group containing up to 4 carbon atoms and the term "alkoxy" refers to an -O-alkyl group. The terms "alkenyl" and "alkynyl" refer to
Refers to unsaturated straight or branched chains containing, for example, 2 to 20 carbon atoms, such as 2 to 6 carbon atoms. Furthermore, the term "aryl" refers to aromatic groups such as phenyl or naphthyl. The terms "cycloalkyl", "cycloalkenyl" and "cycloalkynyl" mean such radicals which are cyclic and which have at least 3, preferably 5-20 ring atoms. The rings may also be joined together to form a bicyclic, tricyclic or larger polycyclic ring system.

The optionally substituted hydrocarbyl group can be substituted with a functional group, or other type of hydrocarbyl group. For example, aryl, heterocycle or cyclic groups such as cycloalkyl, cycloalkenyl or cycloalkynyl may be substituted with hydrocarbyl chains and functional groups such as alkyl, alkenyl or alkynyl groups. When the hydrocarbyl group is itself an alkyl, alkenyl or alkynyl group, it is a heterocyclic group, aryl group, cycloalkyl, cycloalkenyl or cycloalkynyl group which may itself be further substituted with hydrocarbyl or a functional group as described above. Such a cyclic group may be substituted.

[0008]   The term "functional group" refers to halo, cyano, nitro, oxo, C (O) OR.^a, C (O) R^a , OC (O) R^a, OR^a, S (O)_tR^a, NR^bR^c, OC (O) NR^bR^c, C (O) NR ^b R^c, -NR^bC (O) OR^a, -NR^bC (O) R^a, -NR^aCONR^bR^c, = NOR^a,
-N = CR^bR^c, -S (O)_tNR^bR^cOr-NR^bS (O)_tNR^aAnd in the formula, R^a
, R^bAnd R^cAre independently selected from hydrogen or optionally substituted hydrocarbyl
Or R^bAnd R^cAre optionally substituted together, optionally further with sulfur, S (O), S
(O)₂Form a ring containing heteroatoms such as oxygen and nitrogen, and t is 0 or 1-3.
Means a reactive group which is an integer of.   Here, the term "heteroatom" refers to oxygen, nitrogen, cerium or
Refers to non-carbon atoms such as sulfur atoms. If nitrogen atoms are present, they are
, Generally present as part of an amino residue, so substituted with, for example, hydrogen or alkyl
To be done.   The term "amide" generally refers to the formula C (O) NR^bR^cAnd in the formula^bAnd R^cIs hydrogen
Alternatively, it is understood to refer to a group that is an optionally substituted hydrocarbyl group.

[0009]   In particular, the compound of the present invention is a liquid crystal compound of the following general formula (I).

[Chemical 13] Wherein X is O, S or Se and each R ¹ and R ³ is independently cyano, halo, optionally substituted hydrocarbyl, optionally substituted alkoxy, optionally substituted heterocycle, group R ¹³ C (O) O-, wherein R ¹³ is selected from an optionally substituted hydrocarbyl or carboxy or hydrocarbyl ester or amide thereof, provided that at least one or the group R ¹ or R ³ is cyano or Other than halo, each R ² and R ⁴ is independently halo, nitro, lower alkyl optionally substituted with halo,
Or a group R ¹⁴ C (O) O −, wherein R ¹⁴ is an optionally substituted hydrocarbyl, n is 1 or 2, m is 0, 1, 2 or 3, p is 1 or 2, and q is 0 or 1, provided that n + m does not exceed 4 and p + q does not exceed 2, and the compound is DE19
Provided that it is other than the compound described in 90517 or WO98 / 04544.

These compounds have useful liquid crystal properties. In particular, they have a wider nematic phase range than the equivalent biphenyl compounds. They have good dissolution properties,
It is soluble in standard host mixtures and exhibits good mixing properties. For example, in formula (I), when X is O, S or Se, then each R ¹ and R ³ is independently cyano, halo, optionally substituted hydrocarbyl, optionally substituted alkoxy, optionally substituted Heterocycle, or a carboxy or hydrocarbyl ester or amide thereof, provided that at least one or the group R ¹ or R ³ is other than cyano or halo, and each R ² and R ⁴ is independently halo, nitro. A lower alkyl optionally substituted with halo,
Or a group R ¹⁴ C (O) O −, wherein R ¹⁴ is an optionally substituted hydrocarbyl, n is 1 or 2, m is 1, 2, or 3, p is 1 or 2 , And q is 0 or 1,
However, n + m does not exceed 4, p + q does not exceed 2, and the compound is DE1990517.
Alternatively, the compound other than those described in WO98 / 04544 is required.

Preferably, in the compound of formula (I), n is 1 and m is 0, 1 or 2, more preferably 0 or 1, most preferably 0. Preferably p is 1 and q is 0. Suitable lower alkyl groups for R ² and R ⁴ include methyl, fluoromethyl or trifluoromethyl. Preferably, any radicals R ² or R ^{4 present} are halo, especially fluoro. Suitably at most ^two of the radicals R ¹ and R ² are fluoro, preferably the radical R ¹
And at most one of R ² is fluoro. It has been found that the Δε of the mixture containing the fluorinated compound of formula (I) is reduced compared to the mixture containing the non-fluorinated compound of formula (I). Moreover, the presence of fluorine at the R ² position seems to give the mixture more negative behavior. Applicants have shown that when the group (R ² ) _m is fluorine, the compound exhibits only a nematic phase,
And has no smectic phase, and in all cases the mixture is a cyano-equivalent mixture.
It was also found to be much reduced based on PBS22.

When R ² or R ⁴ is of the formula R ¹⁴ C (O) O—, R ¹⁴ is suitably alkyl, cycloalkyl or aryl, preferably alkyl or aryl. Preferably, at least one of R ¹ or R ³ is cyano, especially when low Δε is required. In a particularly preferred embodiment ^one of R ¹ or R ³ is cyano or halo and the other is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl, optionally substituted Cycloalkynyl, optionally substituted aryl, optionally substituted heterocycle, carboxy or esters thereof. For example, ^one of R ¹ or R ³ is cyano or halo and the other is optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted A heterocycle, carboxy or an ester thereof.

Suitably R ¹ or R ³ are optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted, unless they are other than cyano or halo. Selected from aryl, optionally substituted cycloalkyl, optionally substituted cycloalkenyl or optionally substituted cycloalkynyl. Suitable substituents for alkyl, alkenyl, alkynyl, groups R ¹ and R ³ include functional groups as defined above, and aryl, cycloalkyl, heterocycle, all of which are alkyl, alkenyl or alkynyl and It may be substituted with a functional group as defined. Suitable substituents for the aryl, heterocycle, cycloalkyl, cycloalkenyl or cycloalkynyl, groups R ¹ and R ³ are the substituents listed for the alkyl, alkenyl and alkynyl groups, and any functional groups and aryl groups. , A heterocyclic group or an alkyl, alkenyl or alkynyl optionally substituted with a cycloalkyl, cycloalkenyl or cycloalkynyl group.

Preferably R ¹ and R ³ , when they are other than cyano or halo, are optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl,
It is selected from optionally substituted aryl, optionally substituted heterocycle, carboxy or its hydrocarbyl ester. When these are carboxyester groups, they are preferably alkylesters or arylesters such as phenylesters, which phenyl groups may be optionally substituted, for example with alkyl, alkoxy or cyano groups.

When R ¹ or R ³ is other than cyano or halo, suitable R ¹ or R ³ is represented by the following formula (i), (
ii), (iii), (iv), (v), (vi), (vii) or (viii).

[Chemical 14]

[0016]

[Chemical 15] In the formula, X is 0 or 1, R ¹⁰ is a C _1-20 alkyl group, and y and z are independently selected from 0, 1 or 2.

Preferably at least one of the R ¹ or R ³ groups is a group of sub-formulas (i) to (viii) above. If R ¹ or R ³ is other than cyano or halo, particularly preferred groups for R ¹ or R ³ is phenyl substituted cycloalkyl or optionally substituted optionally, is especially optionally substituted phenyl . Suitable substituents for the cycloalkyl or phenyl groups R ¹ and R ³ are substituted with halo, alkyl, especially alkoxy such as C _3-9 alkyl, C _3-9 alkoxy, cyano or itself alkyl or cyano. Good phenyl. Particularly suitable substituents include alkyl, especially C _3-9 alkyl, alkoxy such as C _3-9 alkoxy, cyano or phenyl which may itself be substituted with alkyl or cyano. When R ¹ or R ³ is a group of the formula R ¹³ C (O) O −, R ¹³ is preferably alkyl,
Cycloalkyl or aryl, preferably cycloalkyl.

[0018]   R as cyano¹Or R³Which of these choices you make has a significant impact on the properties of the compound.
You can. For example, R¹Is a cyano compound, R³Is significant compared to cyano compounds
Have different dielectric anisotropies. The birefringence of a mixture containing the compound of the invention is R ¹ R rather³It was also found to be low for cyano.   Preferably X is oxygen or sulfur, most preferably oxygen.   Suitably the substituents are arranged to provide a favorable dipole on the compound. This
For the purposes of, the substituents are preferably curved or wedge-shaped in the overall shape of the molecule.
Will be arranged. Thus, preferably, when the group X is in position 1, it is bicyclic.
Substituents are located at the 2 and 6 positions of the ring.

[0019]   In particular, the invention provides compounds of general formula (IA):

[Chemical 16] Wherein X is oxygen, sulfur or cerium, R ^1a and R ^1b are independently hydrogen,
Selected from cyano, halo, optionally substituted hydrocarbyl, optionally substituted heterocycle or carboxy or hydrocarbyl ester or amide thereof, provided that at least one group R ^1a or R ^1b is other than hydrogen; R ¹⁷ or One of R ¹⁸ is cyano, halo, an optionally substituted hydrocarbyl, an optionally substituted heterocycle or a hydrocarbyl ester or amide thereof,
And the other is hydrogen, halo, nitro, lower alkyl optionally substituted with halo, or the group R ¹⁵ C (O) O-, wherein R ¹⁵ is an optionally substituted hydrocarbyl group; R ^2a and R ^{2 2b} is independently hydrogen, halo, nitro, lower alkyl optionally substituted with halo, or the group R ¹⁴ C (O) O −, wherein R ¹⁴ is as defined above; provided that: (i ) At least one group R ^1a or R ^1b or R ¹⁷ or R ¹⁸ is other than cyano or halo; (ii) when X is S, R ¹⁷ is a carboxy or hydrocarbyl ester or ester thereof and R ¹⁸ is Hydrogen and R ^2a and R ^2b are not both fluoro; (iii) when X is O, R ¹ is an optionally substituted hydrocarbyl or carboxy or hydrocarbyl ester or amide thereof and R ^2a is hydrogen. There, and R ^1b and R ^2b and both Fluorine, R ¹⁷ is other than C _1-8 alkyl.

When R ¹⁷ is a group R ¹⁵ C (O) O—, R ¹⁵ is preferably a group R ^{13 as} defined above. If instead R ¹⁸ is a radical of the formula R ¹⁵ C (O) O −, then R ¹⁵ is preferably a radical R ^{14 as} defined above. Preferably, in the compound of formula (IA), R ^2a is hydrogen. Suitably at least one of R ^1b , R ^2b or R ¹⁸ of formula (IA) is fluoro.
However, preferably at most two of R ^1a , R ^2a , R ^2b or R ^1b are fluoro,
Preferably at most one of these groups is fluoro.

Preferably, one of R ^1b or R ^1a or R ¹⁷ or R ¹⁸ of formula (IA) is cyano or halo and said ring on the other ring of the bicyclic ring in formula (IA) At least one of the groups is an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted aryl,
An optionally substituted heterocycle, carboxy or a hydrocarbyl ester thereof. Thus, for example, when R ^1b or R ^1a is halo or cyano, then at least one of R ¹⁷ or R ¹⁸ is optionally substituted alkyl, optionally substituted cycloalkyl,
It is an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted aryl, an optionally substituted heterocycle, carboxy or a hydrocarbyl ester thereof. Conversely, when R ¹⁷ or R ¹⁸ is halo or cyano, at least one of R ^1a or R ^1b is optionally substituted alkyl, optionally substituted cycloalkyl,
It is an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted aryl, an optionally substituted heterocycle, carboxy or a hydrocarbyl ester thereof.

For example, one of R ^1b or R ^1a or R ¹⁷ or R ¹⁸ of formula (IA) is cyano or halo and said group on the other ring in the bicyclic ring of formula (IA) At least one of
It is an optionally substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted aryl, an optionally substituted heterocycle, carboxy or a hydrocarbyl ester thereof. Specific examples of said optionally substituted cycloalkyl, optionally substituted aryl, optionally substituted heterocycle, carboxy or hydrocarbyl esters thereof are:
It is a group of the above formulas (i) to (viii).

[0023]   A particularly preferred group of compounds of the invention is of formula (II):

[Chemical 17] Wherein R ⁵ is a group R ^{3 as} defined for formula (I), one of R ⁷ and R ⁸ is a group R ^{1 as} defined for formula (I) and the other is hydrogen. Or a group R ^{1 as} defined for formula (I); R ⁶ is hydrogen, cyano or fluoro, preferably hydrogen or fluoro, and R ⁹ is hydrogen, cyano or fluoro, where R ^{When 5} is cyano or fluoro, at least one of R ⁷ or R ⁸ is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally Substituted alkoxy, optionally substituted aryl, optionally substituted heterocycle, carboxy or esters thereof; and when one of R ⁷ or R ⁸ is cyano or fluoro and the other is hydrogen, R ⁵ is optional It is a substituted alkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted alkoxy, an optionally substituted aryl, an optionally substituted heterocycle, carboxy or an ester thereof.

Preferred groups R ⁵ and R ⁷ and / or R ⁸ are cyano; fluoro; alkoxy; alkenyl; alkyl, aryl or carboxy alkylaryl esters; arylalkyl, alkenylaryl, where the aryl ring is optionally Optionally substituted with an alkyl group, a functional group such as fluoro or alkoxy, or even with an aryl group optionally itself substituted with an alkyl group; optionally substituted pyrimidinyl, wherein the optional substituents are especially alkyl. Or cycloalkyl optionally substituted, wherein the cycloalkyl ring is optionally substituted with an alkyl group.

[0025]   A particular example of a compound of formula (II) is a compound of formula (IIA):

[Chemical 18] Wherein R ^{5 ′} is cyano or fluoro, preferably fluoro, one of R ^{7 ′} and R ^{8 ′} is hydrogen and the other is an optionally substituted hydrocarbyl group or a heterocyclic group as described above. . Specific examples of substituted hydrocarbyl groups for R ^{7 ′} or R ^{8 ′} are groups of sub-formula (i), (ii), (iii), (vi) or (viii) above. The compounds of formula (IIA) exhibit advantageous properties in terms of UV stability and low sensitivity to ion contamination and are particularly suitable for use in thin film transmitter (TFT) devices.

[0026]   Specific examples of compounds of formula (II) are listed in Table 1 below.

[Table 1]

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

[0030]

[Table 5]

[0031]

[Table 6]

[0032]

[Table 7]

[0033]

[Table 8]

[0034]   In the above table, * represents the point of attachment to the ring structure.   Specific examples of compounds of formula (I) where X is sulfur are listed in Table 2 below.

[Table 9]

[0035]   The compounds of this invention can be prepared by conventional methods which will be apparent to the skilled chemist.   In particular, the compounds can be prepared by adding a substituent to the bicyclic ring.   Thus, for example, a compound of formula (I) is a compound of formula (III):

[Chemical 19] Wherein R ² , R ³ , R ⁴ , X, n, m, p and q are as defined for formula (I) and Z is a leaving group or group B (OH) ₂ . the compound is a compound of formula (IV), R'-Z ' (IV) wherein R ¹ is as has been defined for formula (I), and Z' is when Z is a leaving group Is a group B (OH) ₂ or is a leaving group if Z is B (OH) ₂ and is then reacted with a group R ² , R ³ or R if desired or necessary. It can be prepared by converting ⁴ to a different such group.

Suitable leaving groups for Z or Z ′ include halo such as bromo or iodo, mesylates, tosylates and triflates. The reaction is preferably 1,
It is carried out in the presence of a base such as sodium carbonate or potassium carbonate in an inert organic solvent such as 2-dimethoxyethane. The reaction is preferably carried out in the presence of an inert atmosphere such as a nitrogen atmosphere. Optionally a palladium catalyst such as tetrakis (
There are catalysts such as triphenylphosphine) palladium. The reaction is preferably carried out at an elevated temperature, for example at the reflux temperature of the solvent.

Of course, other substituents may be introduced in a similar manner, and the order in which this is done depends largely on the nature of the substituents and where they are placed on the ring.
In another route, for example, the compound of formula (I) is a compound of formula (V):

[Chemical 20] Wherein R ¹ , R ² , R ⁴ , X, n, m, p and q are as defined for formula (I) and Z is a compound as defined for formula (III). , The following formula (VI
), R ³ —Z ′ (VI), wherein R ³ is as defined for formula (I), Z ′ is reacted with a compound as defined for formula (IV), And thereafter, if desired, any radical R ¹ ,
R ² and R ⁴ can also be prepared by converting to different such groups. Suitable leaving groups Z or Z'and reaction conditions are the same as described above for the reaction between compounds of formula (III) and formula (IV).

Conversion of the groups R ¹ , R ² , R ³ and R ⁴ to different such groups can be accomplished by conventional methods apparent to the skilled chemist. A reaction particularly useful in this context is the conversion of a carboxylic acid ester group such as an alkyl ester, especially an ethyl ester, into a cyano group. This reaction can be accomplished by hydrolysis of the carboxylic acid ester group, followed by conversion of the carboxylic acid formed to the corresponding acid chloride and then to the amide. Dehydration of the amide yields a cyano compound. Each step can be accomplished using conventional chemistry and these are described in the examples below.

The compounds of formula (III) and (V) are preferably prepared by cyclization reactions, as is understood in the art. For example, the compound of formula (III) is a compound of formula (VII):

[Chemical 21] Where X, n and m are as defined for formula (I) and Z is for formula (I
II) is a compound as defined above, having the formula (VIII):

[0040]

[Chemical formula 22] Wherein R ³ is as defined for formula (I) and R ¹² can be prepared by reaction with a compound which is an alkyl group such as ethyl. Then the group R ³
Can be converted to a different such group in a similar manner as described above for the compound of formula (III). Particularly preferred compounds of formula (VIII) are those in which R ³ is a carboxylic ester group, such as an alkyl ester group, which gives rise to the possibility of subsequent modifications as mentioned above. Thus, the preferred compound of formula (VIII) is diethyl bromomalonate.

The reaction is preferably carried out in an organic solvent such as butanone in the presence of a base such as potassium carbonate. The compounds of formula (IV) and (VI) are known or can be prepared by conventional methods. For example, when Z or Z'is a B (OH) ₂ group, these are reacted with the corresponding halo-substituted compound with magnesium and then trimethylborate in an organic solvent such as tetrahydrofuran, and finally the product is hydrochloric acid. It can be prepared by acidifying with a mineral acid such as. Examples of such preparations are described below. Both compounds of formula (XI) and (XII) are known or can be prepared from known compounds by conventional methods.

In an alternative approach, compounds of formula (I) in which q is 0, p is 1 and R ³ is a carboxy group can be prepared by replacing the substituent R ³ with a compound of formula (IX) And

[Chemical formula 23] ^{Wherein, R 2, R 4, X} , m, n and q are as defined for formula (I), and R ^{1 'is} R ¹ or a precursor as defined for formula (I) Incorporation into a compound which is a body; in the presence of a base such as n-butyllithium and an organic solvent such as tetrahydrofuran, together with a carboxylating agent such as Cardice, and then acidifying the product with an acid such as glacial acetic acid. It can be prepared by If desired, the carboxy group can subsequently be converted into a different R ³ group. Suitable precursor groups R ^{1 ′} include groups that can be converted to the desired R ¹ group by conventional chemistry. Thus, examples of such groups are the groups Z or Z'as defined above. Compounds of formula (IX) in which R ^{1 ′} is a group R ¹ (hereinafter referred to as compounds of formula (IXA)) have liquid crystal properties in their own right and thus form a further aspect of the invention.

[0043]   The compound of formula (IX) in which q is 0 is a compound of formula (X):

[Chemical formula 24] Where R², R^Four, X, n and m are as defined for formula (I) and R ^{1 '} Is a compound as defined for formula (IX); cyclization in the presence of polyphosphoric acid
It can be prepared by The reaction is preferably organic such as chlorobenzene.
It is carried out in a solvent at an elevated temperature, for example the reflux temperature of the solvent.

[0044]   The compound of formula (X) is preferably a compound of formula (XI):

[Chemical 25] In the formula, R ^{1 ′} , R ² , X, m and n are the compounds of the following formula (XII), which are compounds represented by the following formula (XII): Z ″ -CH ₂ CR ⁴ (OCH ₃ ) ₂ (XII ) Wherein R ⁴ is as defined for formula (I) and Z ″ is prepared by reacting with a compound that is a leaving group. Suitable leaving groups Z ″ are defined above for the group Z. The reaction is preferably carried out in an organic solvent such as butanone in the presence of a base such as potassium carbonate. Compounds of formula (IX) can be converted to compounds of formula (V) where Z is a B (OH) ₂ group by reaction with trimethylborate in the presence of a base such as n-butyllithium. Subsequent acidification with a mineral acid such as hydrochloric acid yields the desired product. The reaction is preferably carried out in an organic solvent such as tetrahydrofuran, a reaction of this type being exemplified below.

Another cyclization route that can directly lead to the compound of formula (I) in which q is 0 is represented by the following formula (XII
A compound of I),

[Chemical formula 26] ^{Wherein, R 1 ', R 2,} X, n and m are the compounds of as defined above, a compound of formula _{(XIV), HO 2 C-} R 3' (XIV) wherein, R ^{3 'comprises} the reaction of a compound with a group R ³ or a precursor thereof, as defined for formula (I). The reaction is preferably N, N'- in an organic solvent such as dichloromethane.
Dichlorocarbodiimide (DCC) and 4-N, N-dimethylaminopyridine (DMA
It is carried out in the presence of a base such as P). The reaction is preferably carried out under an inert atmosphere such as nitrogen. The precursor group R ^{3 ′} may be similar to the compounds defined for R ^{1 ′} .

[0046]   The compound of formula (XIII) has the following formula (XIV):

[Chemical 27] Where R ^{1 ′} , R ² , X, n and m can be derived from a compound as defined above with triphenylphosphine under the conditions described below.

Various modifications and alterations to these routes will be apparent to those skilled in the art, and all are encompassed by the present invention. The compounds of the present invention can be selected so that their liquid crystal properties, especially nematic / smectic properties, are matched to the desired application. This can be achieved by varying the substituents on the central ring structure, as described above, or by mixing the compound with other compounds of the invention or other different liquid crystal compounds. The mixture is preferably a eutectic mixture. The compounds of the present invention can be mixed with each other to produce useful liquid crystal compounds, which can be used with liquid crystal polymers or other low molecular weight non-polymeric liquid crystal materials.

As will be appreciated, the compounds of the present invention can be used in a wide variety of devices depending on their unique properties. In applications requiring nematic compounds, compounds having a low melting point, a high transition temperature (TN-I (° C.)), a low viscosity and a high dipole moment, for example, giving a high Δε are required. The compounds of the present invention include those having such properties and other properties such as flexoelectric properties. If the melting point is not low enough, this can be lowered by mixing the compounds of the invention with other liquid crystal compounds, in particular different compounds of the invention, to form a mixture, preferably a eutectic mixture. The transition temperature is a compound of the invention containing at least three carbocyclic, heterocyclic or aryl ring systems, eg compounds of formula (I), wherein R ¹ and R ³ are both carbocyclic, heterocyclic or aryl groups. Can be increased by using or including in a mixture.

For trifluoroterphenyl (TFT) devices, compounds of the invention are preferably selected that have TN twisted nematic values on the order of 90 °. It is an indicator of the degree of twist present in the molecular array. Viscosity (Δn) of such compounds
Are preferably low and for this reason compounds having saturated substituents are preferred.
The compound should have a positive Δε that is the result of the dipole moment along the long axis. The modulus value, K ₁₁ / K _33, is preferably high, but the conductivity is preferably low.
To achieve these latter requirements, halo substituents such as fluoro are preferred over cyano substituents. The compounds of the present invention have so-called "super twisted nematic" properties with TN values on the order of 240-270 °. Such compounds generally have high Δn values,
And may contain an aromatic ring. They have a positive Δε and a high value of K ₁₁ / K ₃₃ , giving sharp tolerance limits.

Liquid crystal devices comprising a mixture of the compounds of the invention form a further aspect of the invention. Examples of such devices include optical and electro-optical devices, magneto-optical devices and devices that respond to stimuli such as temperature changes and total or partial pressure changes. The compounds described above may be included in a mixture, the mixture including at least two compounds. Typical mixtures include mixtures of the above compounds, and also mixtures containing at least one of the above compounds and at least one of the different liquid crystal compounds.

When the smectic A-phase compound of the present invention is composed of chiral molecules, it may exhibit an electroclinic effect, ie a molecular tilt of direct coupling to the applied field. The origin of the electroclinic effect in the smectic A phase composed of chiral polar molecules is described by Garoff and Meyer as follows. When an electric field is applied in parallel to the smectic layer of the smectic A phase, the free rotation of the molecular dipole on the abscissa is biased, and molecular polarization of the non-zero averaged abscissa component is generated. When such a dipole moment exists and is bound to the chirality of the molecule, a long molecular axis (director) tilt is caused in a plane perpendicular to the dipole moment. In samples with a smectic layer that is thin, for example 1 to 3 μm, and inclined or perpendicular to the glass plate, the electroclinic effect can be detected at low applied fields.

In aligned smectic A samples, the tilt of the director is directly related to the tilt of the optical axis. The electroclinic effect results in a linear electro-optical response. The electro-optic effect can itself be expressed as an adjustment of the effective birefringence of the device. Electroclinic (EC) devices are useful, for example, in spatial light modulators that have an output that varies linearly with applied voltage. Further advantages of EC devices are:
It has a much faster fast response time than twisted nematic type devices. E
Known devices of the ferroelectric type are bistable, in contrast to C devices which are not bistable and have an output that varies linearly with applied voltage.

The electroclinic effect, sometimes called the soft-mode effect, is
See dersson et al., Appl. Phys. Lett., 51, 9, (1987). In general terms for the electroclinic effect, it is advantageous if a large slope occurs when a small voltage is applied. An increase in the induced slope results in an increase in contrast ratio. It is also advantageous if a large induced slope can be obtained with a voltage as small as possible. Further, it is advantageous if the correlation between the induced gradient of the molecule and the applied voltage is temperature-dependent. A test substance is generally said to exhibit a saturation voltage effect if there is little or no change in the induced slope when the applied voltage is increased.

D = (2m + 1) λ 4 (Δn) There are various electroclinic devices that can incorporate the compounds of the present invention. For example, in liquid crystal cells active black surface drive can be utilized. One of the walls forming the cell may be formed from a silicon substrate, eg, a wafer having electrical circuitry that drives the pixels. In many of these devices, there is an optimum cell thickness related to birefringence (Δn) by the above equation. Where λ = wavelength of operation Δn = birefringence of liquid crystal material m = integer. Some suitable methods of driving the electroclinic device described in this invention are described in British patent application GB-2247972A. Modes of operation of these devices include amplification regulation or phase regulation. Similar devices can be used in reflective or transmissive modes. S _A ^* means the S _A phase containing a certain proportion of chiral molecules, therefore it is preferred that the compounds of the invention are thus chiral.

Cholesteric or chiral nematic liquid crystals have a twisted helix structure and can respond to changes in temperature by changing the length of the helix pitch. Therefore, when the temperature changes, the wavelength of the light reflected from the planar cholesteric structure changes, and when the reflected light includes a variable range, a clear color change occurs with the temperature change. This means that it has many potential applications, including in the areas of thermography and thermooptics. The cholesteric mesophase differs from the nematic phase in that in the cholesteric phase the director is not constant in space, but undergoes a helical strain. The pitch length of the helix is a measure of the distance the director rotates through 360 °. As the name implies, cholesteric substances are chiral substances. The chiral compounds of the present invention exhibit a helical mesophase and can be used in thermographic or thermooptic applications. The chiral compounds of the present invention can also be used as dopants in electro-optical displays, for example they can be used in twisted nematic displays to eliminate reverse twist defects. They can also be used in cholesteric-> nematic dyed phase change displays and can be used to prevent wave-guiding and enhance contrast.

Thermochromic applications of cholesteric liquid crystal materials are usually visualized against a black background using thin film preparations of the materials. These temperature sensitive devices can be placed in many applications including thermometry, medical thermography, non-destructive testing, radiation detection and decorative purposes. Examples of these are DG McDonnell, Thermotropic Liq
uid Crystals, Critical Reports on Applide Chemistry G, Volume 22, edited by DW Gray, 1987, pp120-44; this reference also contains a general description of thermochromic cholesteric liquid crystals. Generally, commercial thermochromic applications require the formulation of mixtures with low melting points, short pitch lengths and smectic transitions below the required temperature sensitive region.
Preferably the mixture or material should retain a low melting point and a high smectic-cholesteric transition temperature.

Thermochromic liquid crystal devices generally have a thin film of cholesterogen sandwiched between a transparent support substrate and a black absorbing layer. One of the manufacturing methods is
Encapsulating the liquid crystal in a polymer to produce an "ink" having the liquid crystal and applying it to a supporting substrate using printing techniques. Examples of the method for producing this ink include gelatin microencapsulation, US Pat. No. 3,585,318 and polymer dispersion, and US Pat. Nos. 1,161,039 and 3,872,050. One method of preparing well-ordered thin film structures of cholesteric liquid crystals involves laminating the liquid crystals between two embossed plastic sheets. This method is described in British Patent No. 2,143,32
It is described in No. 3.

Other compounds of the present invention or mixtures thereof may be used in ferroelectric mixtures and devices. In particular, the compounds of the present invention can be used in many known forms of liquid crystal display devices, such as chiral smectic electro-optical devices. Such a device may include a layer of liquid crystal material contained between two spaced cell walls holding the electrode structure and the surface treated to align the liquid crystal material molecules. The ferroelectric smectic liquid crystal material may be manufactured by mixing an achiral host and a chiral dopant, and utilizes the tilted chiral smectic C, F, G, H, I, J and K phase ferroelectric properties. The chiral smectic C phase is designated as S _C ^* and the asterisk indicates chirality. The S _C phase is generally considered the most useful because it is the least viscous. Ferroelectric smectic liquid crystal materials should ideally have the following properties: low viscosity, should contain controllable spontaneous polarization (Ps) and ambient temperature, and exhibit a wide range of chemical and photochemical stability. S _C phase that persists over temperature range. Materials with these properties offer the potential for very fast switching liquid crystal containing devices. For some applications of ferroelectric liquid crystals, see JS Pate
l and JW Goodby, Opt. Eng., 1987, 26, 273.

In a ferroelectric liquid crystal device, the molecules switch between different alignment directions depending on the polarity of the applied electric field. These devices can be arranged to exhibit bistable tendency, where the molecule tends to stay in one of two states until switched to the other switching state. Such devices are disclosed, for example, in US5061047 and US4367924.
And as described in US4563059, it is termed a surface-stabilized ferroelectric device. This bistable allows multiple addressing of very large and complex devices. One typical multiple display has display elements, ie, pixels arranged in an X, Y matrix format of the display, for example for alphanumeric characters. The matrix format is provided by forming electrodes on one side as a series of row electrodes and electrodes on the other side as a series of column electrodes. The intersection between each row and column forms an addressable element or pixel. Other matrix layouts are known, for example the Seven Bar numeric display.

There are many different multiple addressing schemes. A common feature involves applying voltage to each column or row in sequence and is called the strobe voltage. At the same time as the strobe voltage applied to each column, an appropriate voltage called the data voltage is applied to all row electrodes. The difference between the different schemes lies in the state of the strobe voltage and data voltage waveforms. Other addressing schemes are GB-2,146,473-A; GB-2,173,336-A; GB-2,173,3
37-A; GB-2,173629-A; WO89 / 05025; Harada et al., 1985, SIDPaper 8.4, pp131-134.
Largerwall et al., 1985, IDRC, pp 213-221 and Maltese et al., Proc 1988 IDRC, pp.
90-101, Fast Addressing for Ferroelectric LC Display Panels.

The material is switched between its two states with two strobe pulses of opposite sign associated with the data waveform. Alternatively, a blanking pulse can be used to switch the substance to one of its states. Periodically, the signs of the blanking pulse and strobe pulse are alternated to maintain a net dc value. Since these blanking pulses are typically larger in magnitude and length of application than the strobe pulses, the material is
It switches regardless of the data waveform. Blanking pulses are applied to the rows on a row basis before the strobe, or the entire display is blanked at one time, or 1
Group rows can be blanked at the same time.

In order to achieve high performance from the device, it is important to use a mixture of compounds that gives a material having optimal ferroelectric smectic properties for a particular type of device. Are well known in the art. The device can be evaluated for speed by considering the response time vs. pulse voltage curve. This relationship shows the minimum value of the switching time (t _min ) at a specific applied voltage (V _min ). In higher or lower voltage than V _min, Suitchingu time is longer than t _{m in.} It is well understood that devices with such a minimum response time vs. voltage curve can be driven multiple times with higher power with higher contrast than other ferroelectric liquid crystal devices. The minimum value of the response time versus voltage curve should occur at low applied voltage and short pulse length, allowing the device to be driven by a low voltage source and a fast frame address refresh rate, respectively.

For typical known materials that do not allow such a minimum when included in a ferroelectric device (which is a mixture of compounds with suitable liquid crystal properties), SCE1
3 and ZLI-3654, both commercially available materials known as Merck UK Ltd, Poole, Dorset. Devices which do not exhibit such a minimum value are in accordance with PCT GB 88/01004 and are for example commercially available SCE8 (Merck UK
Ltd). Another example of prior art material is PCT / GB 86/0
0040, PCT GB 87/00441 and UK 2232416B.

Certain compounds of the present invention are useful in laser addressing applications where a laser beam is used to scan the surface of a material, or leave a writing print on it. For various reasons, many of these materials are composed of organic materials that are at least partially transparent in the visible region. This technique relies on the localized absorption of laser energy to localize heating, which in turn alters the optical properties of another transparent material within the region in contact with the laser beam. In this way, the beam passes through the material, leaving behind a writing print of its path. One of the most important of these applications is in laser addressed optical storage and in laser addressed projection displays where light is directed through cells containing this material and projected onto a screen. Such devices are described by Khan Appl. Phys. Lett. Vol. 22, p111, 1973; and Harold and Steel.
Proceedings of Euro display 84, pages 29-31, September 1984, Paris, France, the material of this device was a smectic liquid crystal material. Devices that use liquid crystal materials as optical storage media are an important class of such devices.
The use of semiconductor lasers, in particular Ga _x Al _1-x As lasers, wherein x is 0 to 1, preferably 1, means that they are invisible and therefore interact with the visual display. It proved to be popular in these applications because it can provide laser energy in the near-infrared wavelength range, which is not possible, yet provide a useful source of distinctly intense thermal energy. Gallium arsenide laser is about 850n
It gives a laser beam having a wavelength of m and is useful for the above applications. If the Al content increases (x
<1), the laser wavelength is reduced to about 750 nm. Storage density can be increased by using short wavelength lasers.

Accordingly, some compounds of the present invention are suitable as optical storage media and may be used in combination with dyes in laser addressing systems, such as optical recording media. The compounds of the invention can also be used in pyroelectric devices such as detectors, steering arrays and vidicon cameras. The pyroelectric detector consists of at least one pixellated electrode plate. In operation, the detector is exposed to radiation R, eg infrared radiation, which is absorbed by the electrodes. This results in an increase in the temperature transmitted by conduction to the layer of pyroelectric material. The change in temperature results in thermal expansion and an electrical charge. This change in charge is usually low compared to the charge output due to Ps with spontaneous polarization changes, temperature changes; this constitutes the main pyroelectric effect. The change in charge results in a change in potential difference between the electrodes. The charge on each pixel is read out and the resulting signal is used to adjust the operating circuitry, for example in a video monitor and for the visible image of an infrared scan.

The selective reflective properties of the materials described in this invention also allow them to be used in inks and paints, and therefore they are also useful in anti-counterfeiting operations. Is. They can also be used in so-called security inks. Other applications include thermal control management, where the material can be included in a coating applied to one or more windows, for example to reflect infrared radiation. Spatial light modulators usually have two glass walls and 0.1-10 μm, for example 2.5 μm
It includes a liquid crystal cell formed of thick spacers. The inner surface of the wall carries a thin transparent indium tin oxide electrode connected to a variable voltage source. On the top of the electrode, for example, there is a surface alignment layer of polished polyimide which will be described in detail later. Other alignment techniques, such as S
non-abrasive methods, such as evaporation of iO ₂ are also suitable. A layer of liquid crystal material is contained between the wall and the spacer. At the front of the cell is a linear polarizer; at the back of the cell is a quarter corrugated plate (which can be arbitrary) and a mirror. An example of a linear polarizer is a polarized beam slitter (not described here).

Suitable devices that can incorporate the substance of the present invention include beam steering,
Included are shutters, modulators and pyroelectric and piezoelectric sensors. The materials of the present invention are also useful as dopants in ferroelectric liquid crystal devices and can be multiplexed or used in active backside ferroelectric liquid crystal systems. The substance of the present invention is also useful as a host substance. The materials of the present invention can be included in mixtures that also contain one or more dopants. Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 Preparation Step 1 of Compound 3 in Table 1 Preparation of 1 -Bromo-4- heptylbenzene Anhydrous aluminum chloride (19.8 g, 148 mmol) was dried with dry dichloromethane (135 ml).
Medium heptanoyl chloride (24.2 g, 163 mmol) was added to a stirred solution. A solution of bromobenzene (21.2 g, 135 mmol) in dry dichloromethane (45 ml) was added and the mixture was refluxed overnight with exclusion of moisture. The reaction was monitored by glc analysis. Cool the mixture in an ice / water bath and, with stirring, poly (methylhydrosiloxane) (21.7 g, 360 mmol)
Was added drop by drop. The mixture was refluxed overnight and glc analysis showed complete conversion of the ketone. After removing the solvent in vacuo, the residue was poured into an ice / water mixture and sodium hydroxide solution (10%) was added to facilitate layer separation and remove residual acid chloride. Ether was added and the separated aqueous layer was washed with ether (2 x 200ml). The combined organic layers with sodium hydroxide solution (10%), washed with water and brine, dried (MgSO ₄₎
. After removing the solvent in vacuum and purifying by flash chromatography [silica gel / petroleum fraction (boiling point 40 to 60 ° C.)], vacuum distillation was performed. A colorless oil was obtained. Yield: 15.1g (44%), Boiling point: 0.1mmHg 117 ° C ¹ H NMR CDCl ₃ / δ 7.38 (2H, d), 7.04 (2H, d), 2.54 (2H, t), 1.57 (2H, qui) 1.28 (8H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2930,1490,1073,828,799 MS m / z 256,254 (M ⁺ ), 199, 185, 171 (100%), 90

Step 2 Preparation of 4-heptylbenzene boric acid In tetrahydrofuran (80 ml) 1-bromo-4-heptylbenzene (20.
2 g, 78 mmol) was added in one portion to oven dried magnesium (2.2 g, 90 mmol) in dry tetrahydrofuran (100 ml) with stirring under nitrogen. Crystals of iodine were added and the mixture was refluxed (2.5 hours) then cooled to room temperature. Dry tetrahydrofuran (80ml) was added and the mixture cooled to -40 ° C. Trimethylborate (16.21 g, 156 mmol) was added dropwise while maintaining the temperature below -10 ° C. The mixture was allowed to come to room temperature and hydrochloric acid (5M, 36 ml) was added with stirring (45 min). The mixture was poured into water and ether was added. The separated aqueous layer was washed twice with ether (2 × 200 ml) and the product was extracted from the mixed ether phase as the sodium salt by washing with potassium hydroxide (2M, 40 ml). The base solution was washed with ether and acidified to pH 3 by adding hydrochloric acid (conc.) To the aqueous solution to liberate the product.
The product was extracted with ether (2 x 200 ml), washed with water and brine, dried (M
MgSO _4), removed the solvent in vacuo. A light brown solid was obtained. Yield: 15.8 g (92%). MS m / z 220 (M ⁺ ), 192, 135, 122, 107 (100%)

Step 3 Preparation of Ethyl 5-Bromobenzo [b] furan-2-carboxylate 5-Bromosalicylaldehyde (2.0 g, 10 mmol), diethyl bromomalonate (2.0 g, 8.4 mmol), and potassium carbonate (2.5 g , 18mmol) of butanone (3
Reflux in (0 ml) (7 hours). glc analysis showed no further reaction. Upon cooling, the solvent was removed in vacuo and water and dichloromethane were added. The separated aqueous layer was washed twice with dichloromethane (2 × 100 ml), the combined organic layers were dried (MgSO _4). After removing the solvent in vacuo, the residue was recrystallized (ethanol). Pale yellow needle-like crystals were obtained. Yield: 0.9 g (40%), melting point: 58-60 ° C. ¹ H NMR CDCl ₃ / δ 7.82 (1H, d), 7.54 (1H, dd), 7.47 (1H, d), 7.46 (1H, s), 4.46 (2H, q), 1.43 (3H, t) IR ( KBr) ν _max / cm ^-1 1730, 1555, 1310, 1185, 855 MS m / z 268,270 (M ⁺ ), 240, 225 (100%), 196, 169

Step 4 of ethyl 5- (4-heptylphenyl) benzo [b] furan-2-carboxylate
Ethyl 5-bromobenzo [b] furan-2-carboxylate from Preparation Step 3 (2.0 g,
7.4 mmol), sodium carbonate (2.0 g, 18.5 mmol), 1,2-dimethoxyethane (10 ml)
) And water (30 ml) were stirred under nitrogen. Tetrakis (triethylphosphine) palladium (0) (0.3 g, 0.3 mmol) was added, followed by 1.2-dimethoxyethane (20 ml).
4-) 4-Heptylbenzeneboronic acid from Step 2 (2.0 g, 8.9 mmol) was added and the mixture was refluxed (4 h). Completion of reaction was shown by glc analysis. After cooling, the reaction mixture was poured into water and ether was added. The separated aqueous layer was washed twice with ether (2 x
100 ml), the mixed ether layer was washed with water and brine, and dried (MgS
O ₄ ). After removal of the solvent in vacuo, the residue is flash chromatographed [silica gel / petroleum fraction (boiling point 40-60 ° C) (impure); petroleum fraction (boiling point 40-60 ° C), dichloromethane 7: 3 (product)]. Purified. The product was recrystallized (hexane). A colorless needle was obtained. Yield: 1.3 g (48%), melting point: 46-8 ° C. ¹ H NMR CDCl ₃ / δ 7.84 (1H, dd), 7.67 (1H, dd), 7.63 (1H, d), 7.56 (1H, d)
, 7.52 (2H, d), 7.27 (2H, d), 4.46 (2H, q), 2.65 (2H, t), 1.65 (2H, qui),
1.44 (3H, t), 1.33 (8H. M), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 1725, 1560, 1160, 1095 MS m / z 364 (M ⁺ ) (100 %), 279, 264, 251, 220

Step 5 Preparation of 5- (4-heptylphenyl) benzo [b] furan-2-carboxylic acid Potassium hydroxide (0.5 g, 6.8 mmol) in ethanol (30 ml) and water (3 ml),
Ethyl 5- (4-heptylphenyl) benzo {b} furan-2-carboxylate from Step 4 was added (1.2 g, 3.4 mmol) and the mixture was refluxed with stirring (5 min). The solvent was removed in vacuo, water was added to the residue and hydrochloric acid (2M) was added to pH 3
Adjusted to. The white solid that precipitated was filtered, dried in vacuo (CaCl ₂ ) and recrystallized (acetic acid). White fibrous needles were obtained. Yield: 0.7 g (63%) transfer (° C) K 131 SmC 185 N 222 Iso. ¹ H NMR CDCl ₃ / δ 7.88 (1H, dd), 7.74 (1H, dd), 7.74 (1H, d), 7.67 (1H, d
), 7.54 (2H, d), 7.28 (2H, d), 7.27 (1H, s), 2.66 (2H, t), 1.65 (2H, qui
), 1.33 (8H, m), 0.89 (3H, m) IR (KBr) ν _max / cm ^-1 2950, 2850, 1690, 1575, 1310, 1170, 805 MS m / z 336 (M ⁺ ), 292, 251 (100%), 231, 207

Step 6 Preparation of 5- (4-heptylphenyl) benzo [b] furan-2-carboxamide 5- (4-heptylphenyl) benzo [b] furan-2-from Step 5 in dry benzene (25 ml) Carboxylic acid (0.70 g, 2.1 mmol) and thionyl chloride (0.75 g, 6.3 mmol)
Was refluxed with exclusion of water. The solvent was removed in vacuo and the crude acid chloride was dissolved in dry tetrahydrofuran (20ml). Ammonia with stirring (d0.880, 0.7 ml)
Was added. After stirring for another 30 minutes, water (40 ml) was added, the precipitate was filtered and washed with cold water. Recrystallize it (ethanol) and dry in vacuum overnight (CaCl ₂ ).
. White crystals were obtained. Yield: 0.55 g (78%), melting point: 201-2 ° C. ¹ H NMR CDCl ₃ / δ 7.86 (1H, dd), 7.66 (1H, dd), 7.56 (1H, d), 7.56 (1H, d)
7.53 (2h, d), 7.27 (2H, d), 6.54 (1H, s), 5.65 (1H, s) 2.66 (2H, t), 1.
66 (2H, qui), 1.31 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 3471, 3396, 3183, 2922, 2849, 1661, 1616, 1395, 801 MS m / z 335 (M ⁺ ), 250 (100%), 191, 178, 165

Step 7 Preparation of 2-Cyano-5- (4-heptylphenyl) benzo [b] furan (Compound 3) Thionyl chloride (1.8 g, 15 mmol) was treated with dry N, N-dimethylformamide (10 ml) in the intermediate step. 5- (4-heptylphenyl) benzo [b] furan-2-carboxamide (from 6
0.5 g, 15 mmol) was added under nitrogen to a stirred solution. The mixture was stirred overnight then ice /
Poured into a water mixture. The product was extracted with ether (2 × 100 ml), the combined extracts were washed with water and saturated sodium bicarbonate solution, dried (MgSO _4). The solvent was removed in vacuo and the product was purified by flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C), dichloromethane 1: 1] and recrystallized (ethanol).
. Colorless crystals were obtained. Yield: 0.3 g (63%). Purity (hplc)> 99%. Transition (℃) K 31.1 N 60.5 Iso. ¹ H NMR CDCl ₃ / δ 7.83 (1H, d), 7.73 (1H, dd), 7.60 (1H, d), 7.51 (2H, d),
7.50 (1H, s), 7.28 (2H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.33 (8H, m),
0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2920, 2850, 2230, 1460, 1130, 885, 800 MS m / z 317 (M ⁺ ), 232 (100%), 203, 190, 176

Example 2 Preparation Step 1 of Compound No. 25 in Table 1 Preparation of 5-bromobenzo [b] furan-2-carboxylic acid The title compound was prepared by using ethyl 5-bromobenzo {b} furan-2-carboxy as a starting material. Rate (prepared as described in Example 1, Step 3) (27.5 g, 102 mmol)
Was prepared and purified by a method similar to that described in Example 1, step 5, except that potassium hydroxide (11.5 g, 204 mmol) was used. White crystals were obtained. Yield: 16.6 g (68%), melting point> 290 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.80 (1H, dd), 7.49 (1H, dd), 7.44 (1H, d), 7.38 (1H,
d) IR (KBr) ν _max / cm ^-1 3417, 1738, 1556, 1395, 1051, 946, 873, 803, 779 MS m / z 241 (M ⁺ ), 223, 169, 89, 62 (100%)

Step 2 Preparation of 5-Bromobenzo [b] furan-2-carboxamide 5-Bromobenzo [b] furan-2-carboxylic acid from Step 1 (16.5 g, 69 mmol),
Thionyl chloride (24.4 g, 205 mmol) and ammonia (d 0.880, 46 ml) were added to Example 1
Converted to 5-bromobenzo [b] furan-2-carboxamide in a similar manner as described in step 6. White needles were obtained. Yield: 9.9 g (60%), melting point: 212-215 ° C. ¹ H NMR DMSO-d ⁶ / δ 7.80 (1H, d), 7.51 (1H, d), 7.40 (1H, dd), 7.32 (2H, s
), 6.95 (1H, d) IR (KBr) ν _max / cm ^-1 3024, 2860, 1591, 1563, 1473, 1318, 1179, 789, 422 MS m / z 240 (M ⁺ ), 223, 169, 89 , 62 (100%)

Step 3 Preparation of 2-Cyano-5-bromobenzo [b] furan 5-Bromobenzo [b] furan-2-carboxamide (9.8 g, 41 mmol) prepared as described in step 2 was used in Example 1 step. Reacting by a method similar to that described above under 7 gave 2-cyano-5-bromobenzo [b] furan. Off-white needles were obtained. Yield: 4.6 g (51%), melting point: 152.5-153.5 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.86 (1H, dd), 7.63 (1H, dd), 7.47 (1H, dd), 7.46 (1H,
d) IR (KBr) ν _max / cm ^-1 2230, 1552, 1437, 1183, 949, 810, 571, 478 MS m / z 223, 221 (M ⁺ ) (100%), 142, 114, 87, 58

Step 4 Preparation of 1-bromo-4-propylbenzene Bromobenzene (31.4 g, 200 mmol), propionyl chloride (22.2 g, 240 mmol),
Ammonium chloride (29.5g, 220mmol), poly (methylhydrosiloxane) (32.1g
, 533 mmol) was treated with 1-bromo-4- by a method similar to that described in Example 1, step 1.
Converted to propylbenzene. A colorless liquid was obtained. Yield: 19.2g (48%), Boiling point: 0.03mmHg, 115 ° C. ¹ H NMR CDCl ₃ / δ 7.38 (2H, d), 7.05 (2H, d), 2.51 (2H, t), 1.61 (2H, sx
t), 0.92 (3H, t) IR (KBr) ν _max / cm ^-1 2965, 2871, 1489, 1077, 1011, 828, 796 MS m / z 200, 198 (M ⁺ ), 169 (100%), 119, 103, 90

Step 5 Preparation of 4-propylbenzeneboric acid 1-Bromo-4-propylbenzene (11.0 g, 55 mmol) obtained in step 2, magnesium (1.5 g, 61 mmol), trimethylborate (11.4 g, 110 mmol) Example 1
Reacted by a method similar to that described in step 2. An off-white solid was obtained. Yield: 7.5 g (83%). MS m / z 164 (M ⁺ ), 147, 135, 91, 43 (100%)

[0080] Step 6 2-Cyano-5- (4-propylphenyl) benzo [b] furan was obtained as described in Preparation above step 3 (Table 1 of Compound 25) 2-cyano-5-bromobenzo [ b] Franc (1
0.0 g, 4.5 mmol), 4-propylbenzeneboronic acid (0.9 g, 5.4 mmol) obtained as described in step 5 above, sodium carbonate (1.2 g, 11.3 mmol), tetrakis (triethylphosphine) palladium (0 ) (0.3 g, 0.3 mmol) was reacted by a method similar to that described in Example 1, step 4, to give compound 25 of Table 1 as white crystals. Yield: 0.3 g (26%). Purity (hplc)> 99%. Transition (℃) K 58.0 (48.9 N) Iso. ¹ H NMR CD ₂ l ₂ / δ 7.86 (1H, dd), 7.75 (1H, dd), 7.62 (1H, d), 7.55 (1H, d
), 7.52 (2H, d), 7.29 (2H, d), 2.64 (2H, t), 1.67 (2H, sxt), 0.97 (3H,
t) IR (KBr) ν _max / cm ^-1 2962, 2871, 2229, 1560, 1460, 1266, 1126, 885, 801,
612 MS m / z 261 (M ⁺ ), 232 (100%), 203, 176, 151

Example 3 Preparation Step 1 of Compound 26 in Table 1 Preparation of 1 -bromo-4- pentylbenzene Bromobenzene (21.2 g, 135 mmol), valeryl chloride (19.7 g, 163 mmol), ammonium chloride (19.8 g, 148 mmol) ), Poly (methylhydrosiloxane) (21.7 g, 360
mmol) was reacted in the same manner as described in Example 1, Step 1, to give 1-bromo-4
-Pentylbenzene was obtained as a colorless liquid. Yield: 11.6g (38%), Boiling point: 0.2mmHg at 100 ℃. ¹ H NMR CDCl ₃ / δ 7.38 (2H, d), 7.04 (2H, d), 2.54 (2H, t), 1,58 (2H, qui
), 1.31 (4H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2858, 1486, 1073, 830, 796 MS m / z 228, 226 (M ⁺ ), 198, 183, 171 (100%), 157

Step 2 Preparation of 4-Pentylbenzene Boric Acid By a method similar to that described in Example 1, Step 2, 1-bromo-4-pentylbenzene (15.2 g, 67 mmol), magnesium (1.9 g) , 77 mmol) and trimethylborate (13.9 g, 134 mmol) to give the title compound. The product was obtained as a waxy white solid. Yield: 6.4 g (50%). MS m / z 522 (3M ⁺ -3H ₂ O), 465 (100%), 409, 352, 175

[0083] Step 3 2-Cyano-5- (4-pentylphenyl) benzo [b] furan was obtained as described in Preparative Example 2 Step 3 (Table 1 of Compound 26) 2-cyano-5- Bromobenzo [b] furan (0.6 g, 2.7 mmol), 4-pentylbenzeneboronic acid from step 2 (0.6 g, 3.2 mm)
ol), sodium carbonate (0.7 g, 6.8 mmol), tetrahydrofuran (triethylphosphine) palladium (0) (0.2 g, 0.1 mmol) together and reacted in a manner similar to that described in Example 1, step 4, The desired compound was obtained as a colorless plate. Yield: 0.3 g (38%). Purity (hplc)> 99%. Transition (℃) K 51.1 N 56.4 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.87 (1H dd), 7.75 (1H, dd), 7.61 (1H, ddd), 7.54 (1H,
d), 7.52 (2H, d), 7.28 (2H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.34 (4H,
m), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 2965, 2861, 2232, 1558, 1439, 1187, 949, 819, 524
MS m / z 289 (M ⁺ ), 232 (100%), 203, 189, 176

Example 4 Preparation Step 1 of Compound 40 in Table 1 Preparation of 1 -Bromo-4-hexylbenzene 1 -Bromo-4-hexylbenzene was prepared by using bromobenzene (21.2 g,
135 mmol), hexanoyl chloride (20.0 g, 149 mmol), ammonium chloride (19.9 g,
149 mmol) and poly (methylhydrosiloxane) (21.7 g, 360 mmol), but prepared and purified in a similar manner as described in Example 1, Step 1. A colorless liquid was obtained. Yield: 10.4 g (32%), Boiling point: 0.01 mmHg, 110 ° C. ¹ H NMR CDCl ₃ / δ 7.38 (2H, d), 7.03 (2H, d), 2.54 (2H, t), 1.57 (2H, qui
), 1.29 (6H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2861, 1489, 1075, 807, 525 MS m / z 242,240 (M ⁺ ), 171 (100% ), 103, 91

Step 2 Preparation of 4-hexylbenzeneboric acid 4-hexylbenzeneboric acid is the product of step 1 (8.0 g, 33 mmol), magnesium (1.0 g, 40 mmol), and trimethylborate (6.9 g, 66 mmol). From a similar method as described in Example 1, Step 2. A light brown solid was obtained. Yield: 4.8 g (71%). MS m / z 564 (3M ⁺ -3H ₂ 0), 535, 507, 493, 117 (100%)

Step 3 Preparation of 2-Cyano-5- (4-hexylphenyl) benzo [b] furan (Compound 40 in Table 1 ) 2-Cyano-5-obtained as described in Example 2, Step 3. Bromobenzo [b] furan (1.0 g, 4.5 mmol), 4-hexylbenzeneboronic acid (obtained as described in step 2 above) (1.0 g, 5 mmol), sodium carbonate (1.2 g, 11 mmol) and tetrakis ( Triethylphosphine) palladium (0) (0.3 g, 0.3 mmol) was reacted together by a method similar to that described in Example 1, step 4. Compound 40 of Table 1 was obtained as colorless crystals. Yield: 0.3 g (22%). Purity (hplc): 99%. Transition (℃) K 25.4 N 45.2 Iso. ¹ H NMR CDCl ₃ / δ 7.83 (1H, d), 7.73 (1H, dd), 7.60 (1H, d), 7.51 (2H, d)
, 7.49 (1H, s), 7.28 (2H, d), 2.66 (2H, t), 1.66 (2H, qui), 1.39-1.31 (6
H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2861, 2235, 1561, 1271, 1128, 951, 808 MS m / z 303 (M ⁺ ), 274, 246, 232 (100%), 219

Example 5 Preparation Step 1 of Compound 36 in Table 1 Preparation of 1 -Bromo-4-octylbenzene The title compound was as described in Step 1 of Example 1 except that the following starting materials were used. Prepared and purified in an analogous manner: Bromobenzene (21.2 g, 135 mmol), nonanoyl chloride (24.2 g, 149 mmol), ammonium chloride (19.9 g, 149 mmol), poly (methylhydrosiloxane) (21.7 g, 360).
mmol). A colorless liquid was obtained. Yield: 16.4g (45%), Boiling point: 0.9mmHg, 158 ℃. ¹ H NMR CD ₂ Cl ₂ / δ 7.37 (2H, d), 7.06 (2H, d), 2.54 (2H, t), 1.56 (2H, qui
), 1.26 (10H, m), 0.86 (3H, t) IR (KBr) ν _max / cm ^-1 2932, 2859, 1489, 1074, 803, 519 MS m / z 270,268 (M ⁺ ), 211, 169 ( 100%), 155, 89

Step 2 Preparation of 4-octylbenzeneboric acid 4-Octylbenzeneboric acid was prepared and purified in a manner similar to that described in Example 1, Step 2, except that the following starting materials were used: 1-Bromo-4-octylbenzene from 1 (6.0 g, 22 mmol), magnesium (0.7 g, 27 mmol), trimethylborate (4.6 g, 44 mmol). A pale yellow solid was obtained. Yield: 4.2 g (82%). MS m / z 648 (3M ⁺ -3H ₂ O), (100%), 551, 452, 353, 187

Step 3 Preparation of 2-Cyano-5- (4-octylphenyl) benzo [b] furan (Compound 36 in Table 1) Compound 36 was prepared as described in Example 1, Step 4 from the following starting materials. Prepared and purified in a similar manner: 4-octylbenzeneboronic acid from Step 2 (2.0 g, 8.5 mmol), 2-cyano-5-bromobenzo [b] furan (obtained as described in Example 2, Step 3). ) (1.6g, 7.1m
mol), sodium carbonate (1.9 g, 18 mmol), tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol). A colorless liquid crystal was obtained. Yield: 0.5 g (21%). Purity (hplc): 98.5%. Transition (℃) K 28.2 SmA 34.3 N 48.8 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.87 (1H, dd), 7.45 (1H, dd), 7.62 (1H, d), 7.55 (1H, d
), 7.53 (2H, d), 7.29 (2H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.35-1.29
(10H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2932, 2859, 2235, 1561, 1464, 1184, 951, 807 MS m / z 331 (M ⁺ ), 260, 232 (100%), 203, 57

Example 6 Preparation Step 1 of Compound 34 in Table 1 Preparation of 1 -Bromo-4-nonylbenzene The title compound was prepared from the following reagents in a similar manner as described in Example 1, Step 1. And purified: bromobenzene (21.2 g, 135 mmol), nonanoyl chloride (26.3 g, 149 mmol), ammonium chloride (19.9 g, 149 mmol), poly (methylhydrosiloxane) (21.7 g, 360)
mmol). A colorless liquid was obtained which solidified on standing to a waxy solid. Yield: 7.0 g (18%), Boiling point: 0.01 mmHg, 145 ° C. ¹ H NMR CDCl ₃ / δ 7.38 (2H, d), 7.04 (2H, d), 2.54 (2H, t), 1.58 (2H, qui
), 1.27 (12H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2934, 2859, 1490, 1074, 825, 798, 634, 510 MS m / z 284,282 (M ⁺ ), 169, 91 (100%), 71

Step 2 Preparation of 4-Nonylbenzeneboric Acid The title compound was prepared and purified in the same manner as described in Example 1, Step 2 from the following reagents: 1-Bromo-from Step 1 4-nonylbenzene (5.0 g, 18 mmol), magnesium (0
0.5 g, 22 mmol), trimethylborate (3.7 g, 33 mmol). A waxy white solid was obtained. Yield: 3.7 g (83%). MS m / z 691 (3M ⁺ -3H ₂ O), 578, 452, 354, 117 (100%)

Step 3 Preparation of 2-Cyano-5- (4-nonylphenyl) benzo [b] furan (Compound 34 in Table 1) Compound 34 was prepared from the following reagents as described in Example 1, Step 4. Prepared and purified in a similar manner: 4-nonylbenzeneboronic acid from step 2 (1.2 g, 5 mmol), 2-cyano-5-bromobenzo [b] furan (obtained as described in Example 2, step 3). () (1.0g, 4.5mmo
l), sodium carbonate (1.2g, l1mmol), tetrakis (triethylphosphine)
Palladium (0) (0.3 g, 0.3 mmol). A colorless needle was obtained. Yield: 0.5 g (32%). Purity (hplc): 98.6%. Transition (℃) K 28.1 SmA 49.6 N 60.0 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.86 (1H, dd), 7.75 (1H, dd), 7.61 (1H, d), 7.55 (1H, d
), 7.52 (2H, d), 7.29 (2H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.31 (12H,
m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2858, 2333, 1464, 1127, 950, 887, 805 MS m / z 345 (M ⁺ ), 231 (100%) 218 , 190, 176

Example 7 Preparation Step 1 of Compound 16 in Table 1 Preparation of 4-Nonyloxybenzeneboric Acid The title compound was prepared in the same manner as described in Example 1, Step 2 using the following reagents. Prepared and purified: 4-nonyloxybromobenzene (5.0g, 17mmol), magnesium (0.5g, 22mmo
l), trimethylborate (3.5 g, 34 mmol). A pale yellow solid was obtained. Yield: 4.0 g (88%). MS m / z 264 (M ⁺ ), 238, 220, 151, 94 (100%)

[0094] described in Step 2 Ethyl 5- (4'-nonyloxyphenyl) benzo [b] furan-2-Karubokishire preparative Preparation of ethyl 5-bromobenzo [b] furan-2-carboxylate (Example 1 Step 3 (1.5 g, 14 mmol), 4-nonyloxybenzene boric acid (1.
8 g, 7 mmol), sodium carbonate (1.5 g, 14 mmol), tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol) were reacted together in a similar manner as described in Example 1, step 4. . Ethyl 5- (4'-nonyloxyphenyl) benzo [b] furan-2-carboxylate was obtained as a white solid. Yield: 0.7 g (31%). Transition (℃) K 85.8 (84.6 SmA) Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.83 (1H, d), 7.66 (1H, dd), 7.62 (1H, d), 7.55 (1H, s)
, 7.54 (2H, d), 6.98 (2H, d), 4.41 (2H, q), 4.00 (2H, t), 1.80 (2H, qui)
, 1.41 (2H, t), 1.30 (12H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2923, 2852, 1722, 1607, 1574, 1517, 1164, 945, 8
39, 747 MS m / z 408 (M ⁺ ), 281, 227, 97, 57 (100%)

Step 3 Preparation of 5- (4-nonyloxyphenyl) benzo [b] furan-2-carboxylic acid 5- (4-nonyloxyphenyl) benzo [b] furan-2-carboxylic acid was prepared using the following reagents. Was prepared and purified in a similar manner as described in Example 1, Step 5: Ethyl 5- (4′-nonyloxyphenyl) benzo [b] furan-2-carboxylate (0.7) from Step 2. g, 1.7 mmol), potassium hydroxide (0.2 g, 3.4 mmol). A white crystalline solid was obtained. Yield: 0.5 g (77%). Transition (℃) K 212.2 SmC 223.0 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.87 (1H, d), 7.72 (1H, dd), 7.69 (1H, s), 7.65 (1H, d)
, 7.54 (2H, d), 6.99 (2H, d), 4.01 (2H, t), 1.80 (2H, qui), 1.48 (2H, m)
, 1.30 (10H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 3420, 2920, 2840, 2547, 1690, 1515, 1174, 942, 748
MS m / z 380 (M ⁺ ), 254 (100%) 225, 210, 180

Step 4 Preparation of 5- (4-nonyloxyphenyl) benzo [b] furan-2-carboxamide The product of Step 3 (0.9 g, 2.4 mmol), thionyl chloride (0.9 g, 7.2 mmol), and ammonia. (D 0.880, 1.4 ml) was used in a similar manner as described in Example 1, Step 6 to give the desired compound as a white crystalline solid. Yield: 0.8 g (82%), melting point: 201-202 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.83 (1H, dd), 7.65 (1H, dd), 7.57 (1H, d), 7.54 (2H, d
), 7.49 (1H, d), 6.99 (2H, d), 6.53 (1H, s), 5.65 (1H, s), 4.00 (2H, t),
1.80 (2H, qui), 1.41 (12H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 3462, 2919, 2851, 1678, 1601, 1518, 1166, 941, 812 MS m / z 379 (M ⁺ ), 253 (100%) 225, 181, 152

Step 5 Preparation of 2-Cyano-5- (4-nonyloxyphenyl) benzo [b] furan ( Compound 16 in Table 1 ) Compound 16 was described in Example 1 Step 7 using the following amounts: Prepared and purified in the same manner as described above. Step 4 product (0.7 g, 1.9 mmol), thionyl chloride (2.3 g, 19 mmol). Colorless plate-like crystals were obtained. Yield: 0.1 g (15%). Purity (hplc): 99.9%. Transition (℃) K 62 SmA 87 N 97 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.80 (1H, d), 7.70 (1H, dd), 1.58 (1H, d), 7.52 (1H, s)
, 7.51 (2H, d), 6.97 (2H, d), 3,98 (2H, t), 1.78 (2H, qui), 1.46 (2H, m)
, 1.28 (10H, m), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 2859, 2236, 1688, 1517, 1182, 1032, 842, 808
MS m / z 361 (M ⁺ ), 248, 235 (100%), 206

Example 8 Preparation Step 1 of Compound 41 in Table 1 2- (4-Pentylcyclohexyl) phenoxy) acetaldehyde dimethyla
Preparation of cetal 4- (4-pentylcyclohexyl) phenol (in cyclopentanone (60 ml)
10.0 g, 41 mmol), bromoacetaldehyde dimethyl acetal (10.1 g, 60 mmo
A mixture of l), potassium carbonate (11.1 g, 80 mmol) and potassium iodide (0.5 g, 3 mmol) was refluxed with stirring under nitrogen (48 hours). The reaction was monitored by glc analysis. After allowing to cool, the mixture was poured into water and ether was added. The separated aqueous layer was saturated with salt and washed with ether (2 x 200 ml). The combined organic layers were washed with sodium hydroxide solution (10%), water, dried (Na ₂ SO ₄ ) and the solvent removed in vacuo. Flash chromatography of the crude product [neutral alumina / petroleum fraction (boiling point
40-60 ° C.) and dichloromethane 1: 1]. A pale yellow liquid was obtained. Yield: 10.1 g (75%), Boiling point: 0.01 mmHg, 195 ° C. ¹ H NNM CD ₂ Cl ₂ / δ 7.11 (2H, d), 6.82 (2H, d), 4.66 (1H, t), 3.94 (2H, d),
3.41 (6H, s), 2.83-2.80 (1H, m), 1.73-1.66 (4H, m), 1.45-1.38 (1H, m),
1.35-1,20 (10H, m), 1.08-1.02 (2H. M), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2928, 2860, 1709, 1644, 1514, 1139, 1081, 828 Ms m / z 334 (M ⁺ ), 260, 176, 133, 75 (100%)

Step 2 Preparation of ethyl 5- (4-pentylcyclohexyl) benzo [b] furan The product of Step 1 (10.1 g, 31 mmol) was added to polyphosphoric acid (13 g) in chlorobenzene (130 ml) which was refluxed with stirring. ) Was added drop by drop. The mixture was refluxed overnight (glc analysis showed the reaction was complete) and allowed to cool. Remove the solvent in vacuo,
Sodium hydroxide solution (10%) and ether were added. The separated aqueous layer was washed with ether (2 × 200 ml), the mixed organic layer was washed with water and brine, and dried (
MgSO _4). The solvent was removed in vacuo and the crude product was flash chromatographed [
Silica gel / petroleum fraction (boiling point 40-60 ° C)] and then distilled. A pale yellow liquid was obtained. Yield: 4.1 g (48%), Boiling point: 0.01 mmHg, 165 ° C. ¹ H NNR CD ₂ Cl ₂ / δ 7.76 (1H, d), 7.34 (1H, d), 7.31 (1H, d), 7.07 (1H, dd
), 6.64 (1H, dd), 2.48 (1H, tt), 1.84-1.77 (4H, m), 1.44 (1H, dd), 1.38
(1H, dd), 1.26-1.14 (9H. M), 1.02 (1H, dd), 0.95 (1H, dd), 0.83 (3H, t)
IR (KBr) ν _max / cm ^-1 2927, 2856, 1514, 1455, 1197, 877, 809, 735 MS m / z 270 (M ⁺ ), 199, 171, 157 (100%), 131

Step 3 Preparation of 5- (4-pentylcyclohexyl) benzo [b] furan-2-carboxylic acid Nitrogen was added to a flask containing the product of Step 2 (1.7 g, 6.3 mmol) in dry tetrahydrofuran (70 ml). It was flushed, degassed and again flushed with nitrogen and cooled (-70 ° C). n-
Butyllithium (2.5 M hexane, 2.7 ml, 6.7 mmol) was added dropwise with stirring and continued at -70 ° C (0.5 hours). Mix the mixture in dry tetrahydrofuran with'Cardic
'Was poured into the stirred slurry and allowed to come to room temperature with continuous stirring. The solvent was removed in vacuum. The residue was dissolved in glacial acetic acid and the resulting solution was poured into water. The solid was filtered, washed with water and dried in vacuum (KOH). A white solid was obtained. Yield: 0.2 g (10%). ¹ H NNR CD ₂ Cl ₂ / δ 7.47 (1H, d), 7.44 (1H, d), 7.39 (1H, s), 7.27 (1H, dd)
, 2.54 (1H, tt), 1.89-1.83 (4H, m), 1.49 (1H, dd), 1.42 (1H dd), 1.31-1.
19 (9H, m), 1.07 (1H, dd), 1.10 (1H, dd), 0.86 (3H, t) (No acidic proton signal was observed) IR (KBr) ν _max / cm ^-1 3100, 2926 , 2853, 1692, 1580, 1425, 943, 828 MS m / z 314 (M ⁺ ), 260, 201, 188 (100%), 175

Step 4 Preparation of 5- (4-pentylcyclohexyl) benzo [b] furan-2-carboxamide The title compound was prepared in the same manner as described in Example 1, Step 6, using the following reagents: Prepared and purified: product of step 3 (0.2 g, 0.6 mmol), thionyl chloride (0.2 g, 1.8 mmol), ammonia (d 0.880, 0.4 ml). Colorless needle-like crystals were obtained. Yield: 0.08 g (50%), melting point: 214-215 ° C. ¹ H NNR CD ₂ Cl ₂ / δ 7.51 (1H, d), 7.43 (1H, d), 7.41 (1H, d), 7.31 (1H, dd
), 6.51 (1H, s, br), 5.69 (1H, s, br), 2.59 (1H, tt), 1.93-1.88 (4H, m),
1.55-1.45 (2H, m), 1.33-1.21 (9H, m), 1.36-1.03 (2H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 34247, 3167, 2926, 2854 , 1659, 1613, 1449, 1198, 9
39, 888 MS m / z 313 (M ⁺ ), 200, 187 (100%), 187, 115

Step 5 Preparation of 2-Cyano-5- (4-pentylcyclohexyl) benzo [b] furan (Compound 41 in Table 1 ) Compound 41 was prepared as described in Example 1, Step 7 using the following reagents. Prepared and purified in a similar manner to: 5- (4-pentylcyclohexyl) benzo [b] furan-2-carboxamide from step 4 (0.05 g, 0.2 mmol), thionyl chloride (0.2 g, 1.4 mmol). A white solid was obtained. Yield: 0.03 g (60%). Purity (hplc)> 99%. Transition (℃) K 77.6 (N 58.5) Iso. ¹ H NNR CD ₂ Cl ₂ / δ 7.51 (1H, dd), 7.47 (1H, ddd), 7.45 (1H, d), 7.39 (1H,
dd), 2.60 (1H, tt), 1.93-1.87 (4H, m), 1.52-1.43 (2H, m), 1.33-1.21 (9H
, m), 1.14-1.03 (2H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2924, 2852, 2230, 1557, 1465, 1198, 950, 874, 845
, 815 MS m / z 295 (M ⁺ ), 252, 224, 182, 169 (100%)

Example 9 Preparation step 1 of compound 42 in Table 1 Preparation of 2- (4-bromophenoxy) acetaldehyde dimethyl acetal 4-butaphenol (87.2 g, 504 mmol), bromoacetaldehyde dimethyl acetal 85.2g, 520mmol), potassium carbonate (71.9g,
A mixture of 520 mmol) and potassium iodide (4.2 g, 25 mmol) was refluxed (48 h) with stirring under nitrogen. The reaction was monitored by glc analysis. After allowing to cool, the mixture was poured into water and ether was added. The separated aqueous phase was saturated with salt and washed with ether (3 x 300 ml). The combined organic layers were washed with sodium hydroxide solution (10%) and water, dried (Na ₂ SO ₄ ) and the solvent removed in vacuo. The crude product was purified by flash chromatography [neutral alumina / dichloromethane] and distilled. Yield: 52.6 g (40%), Boiling point: 0.25 mmHg, 105 ° C. ¹ H NMR CDCl ₃ / δ 7.37 (2H, d), 6.81 (2H, d), 4.70 (1H, t), 3.97 (2H, d)
, 3.45 (6H, s) IR (KBr) ν _max / cm ^-1 2940, 1555, 1485, 1070, 820, 645, 505 MS m / z 262,260 (M ⁺ ), 231, 199, 173, 75 (100% )

Step 2 Preparation of 5-Bromobenzo [b] furan 5-Bromobenzo [b] furan was prepared and purified in a similar manner as described in Example 8, Step 2 using the following reagents: The product of 1 (52.6 g, 202 mmol), polyphosphoric acid (85.0 g). A colorless liquid was obtained. Yield: 20.2g (51%), boiling point: 80 ° C. at ^{0.01mmHg (. Lit 2 15 ℃)} . ¹ H NMR CDCl ₃ / δ 7.72 (1H, dd), 7.61 (1H, d), 7.38 (1H, dd), 6.71 (1H,
d), 7.37 (1H, d) IR (KBr) ν _max / cm ^-1 1440, 1165, 1030, 800, 760, 670, 420 MS m / z 198,196 (M ⁺ ), 168, 155, 117, 89 ( (100%)

Step 3 Preparation of 5-Cyanobenzo [b] furan in N-methylpyrrolidone-2-one (700 ml) Product of Step 2 (20.0 g, 102 mmol)
And a cuprous cyanide monohydrate (22.0 g, 204 mmol) mixture was refluxed with stirring (24 hours). A glc analysis showed the reaction was complete. Allow the reaction mixture to cool and then'Hyflo
It was filtered through a pad of Supercel '. It was poured into water and ether was added. The separated aqueous layer was extracted with ether (2 x 300 ml). The mixed ether layer was washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The desired product was recrystallized from cyclohexane. A colorless needle was obtained. Yield: 6.6 g (45%), melting point: 82-83 ° C. ¹ H NNR CD ₂ Cl ₂ / δ 7.98 (1H, dd), 7.78 (1H, d), 7.61 (1H, d), 7.60 (1H, d
d), 6.89 (1H, dd) IR (KBr) ν _max / cm ^-1 3150, 2200, 1755, 1600, 1550, 1185, 1010, 885, 760
, 610 MS m / z 143 (M ⁺ ), (100%), 88, 62, 50

Step 4 Preparation of 5-cyanobenzo [b] furan-2-boric acid A solution of the product of Step 3 (6.5 g, 45 mmol ) in dry tetrahydrofuran (150 ml) was degassed and flushed with nitrogen. It was cooled (-90 ° C) and n-butyllithium (2.5M in hexane, 19.1ml, 48mmol) was added dropwise with stirring. Stirring was continued (0.5 h) and trimethylborate (9.4 g, 90 mmol) was added at -100 ° C. After stirring (20 minutes), hydrochloric acid (2M, 137 ml) was added and the mixture was stirred for another 5 minutes. After returning to room temperature, the mixture was poured into water and ether was added. The separated aqueous layer was washed with ether (2 x 200 ml). The combined organic layer was washed with water and brine, dried (
MgSO _4), and eliminated in vacuo the solvent. An off-white solid was obtained. Yield: 7.2 g (86%). MS m / z 187 (M ⁺ ), 160, 145, 117, 43 (100%)

Step 5 Preparation of 2- (4-propylphenyl) -5-cyanobenzo [b] furan (Compound 42 in Table 1) The compound was prepared as described in Example 1, Step 4 using the following reagents: And 1-bromo-4-propylbenzene (1.0 g, obtained as described in Example 2, step 4).
, 5 mmol), the product of step 4 (1.1 g, 6 mmol), sodium carbonate (1.3 g, 13 m
mol), tetrakis (triethylphosphine) palladium (0) (0.3g, 0.3mmol
). Colorless crystals were obtained. Yield: 0.1 g (8%). Purity (hplc) 98%. Transition (℃) K 98.0 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.93 (1H, dd), 7.79 (2H, d), 7.61 (1H, d), 7.55 (1H, dd)
, 7.31 (2H, d), 7.06 (1H, d), 2.65 (2H, t), 1.68 (2H, sxt), 0.96 (3H, t)
IR (KBr) ν _max / cm ^-1 2966, 2225, 1505, 1463, 1118, 818, 794, 738 MS m / z 261 (M ⁺ ), 232 (100%), 202, 1762 58

Example 10 Preparation of 2- (4-pentylphenyl) -5-cyanobenzo [b] furan (Compound 27 in Table 1) Compound 27 was prepared as described in Example 1, Step 4, using the following reagents. Prepared and purified in a similar manner to: 1-Bromo-4-pentylbenzene (1.1 g, obtained as described in Example 1, Step 1).
, 5 mmol), 5-cyanobenzo [b] (1.1 g, 6 mmol), sodium carbonate (1.3 g, 13
mmol), tetrakis (triethylphosphine) palladium (0) (0.3g, 0.3mmo
l). Colorless crystals were obtained. Yield: 0.2 g (14%). Purity (hplc)> 99%. Transition (℃) K 99.7 (86.5 N) Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.92 (1H, dd), 7.89 (2H, d), 7.61 (1H, d), 7.55 (1H, d
d), 7.31 (2H, d), 7.05 (1H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.35 (4H,
m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2865, 2224, 1504, 1461, 1185, 1115, 890, 80
0, 740 MS m / z 289 (M ⁺ ), (100%), 245, 232, 202, 219, 203

Example 11 Preparation Step 1 of Compound 13 in Table 1 Preparation of Methyl 3-chloromethyl-4-hydroxybenzoate A suspension of 4-hydroxybenzoate (15.2 g, 100 mmol) in hydrochloric acid (concentrated, 130 ml) was added. Cooled with stirring (5 ° C.). Paraformaldehyde (3.3 g, 11 mmol) was added and the mixture was heated (50-55 ° C). The mixture was left overnight. The solid was filtered and washed with water. The crude product was dried overnight in vacuo (CaCl ₂ ) and recrystallized (CHCl ₃ ). A white solid was obtained. Yield: 8.0 g (40%), melting point: 144-145 ° C, (lit. ³ 147-149 ° C). ¹ H NMR CDCl ₃ / δ 8.03 (1H, d), 7.93 (1H, dd), 6.90 (1H d), 6.18 (1H, s)
, 4.68 (2H, s), 3.90 (3H, s) IR (KBr) ν _max / cm ^-1 3241, 2958, 1688, 1605, 1287, 1152, 844, 754, 705 MS m / z 200 (M ⁺ ) , 165 (100%), 149, 133, 119

Step 2 2-hydroxy-5- (methoxycarbonyl) benzyltriphenylphosphonium
Preparation of chloride A mixture of the product of step 1 (7.9 g, 39 mmol) and triphenylphosphine (9.8 g, 37 mmol) in chloroform (100 ml) was refluxed (1 hour). The mixture was cooled and the solvent removed in vacuo. The residue was washed with toluene and solidified. After filtration from toluene, the product was heated in vacuum (100 ° C., 1 hour) and recrystallized (H ₂ O).
. Colorless crystals were obtained. Yield: 13.8 g (81%), melting point: 256-7 ° C. ¹ H NMR CDCl ₃ / δ 11.37 (1H, s), 7.76 (3H, dt), 7.66 (1H, ddd), 7.59 (12
H, m) 7.38 (1H, d), 7.38 (1H, d), 4.71 (2H, d), 3.76 (3H, s) IR (KBr) ν _max / cm ^-1 3400, 1693, 1606, 1435, 1291 , 1113, 770, 745, 690 MS m / z 426 (M + -Cl -), 395, 349, 262 (100%), 183

Step 3 Methyl 2- (4-heptylphenyl) benzo [b] furan-5-carboxylate (
Preparation of compound 11) in Table 1 N, N'-dicyclohexylcarbodiimide (1.
8 g, 9 mmol) in dry dichloromethane (80 ml), N, N '-(dimethylamino) pyridine (0.2 g, 1.6 mmol), the product of step 2 (3.2 g, 6.8 mmol) and 4-heptylbenzoic acid ( 1.8 g, 8 mmol) was added to the stirred mixture. Stirring was continued (24 hours) and dry toluene (350 ml) was added. Dichloromethane was distilled in a stream of nitrogen. Dry triethylamine (2.0 g, 20 mmol) was added and the mixture was heated with stirring under nitrogen (85
(° C) (14 hours). The analysis showed a complete reaction. After cooling, the mixture was filtered and the solvent removed in vacuo. The residue was subjected to flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C.), dichloromethane 6: 4] and recrystallized (hexane). Colorless plate-like crystals were obtained. Yield: 1.3 g (55%). Transition (℃) K 101 SmF 104.5 SmA 114.9 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 8.30 (1H, dd), 7.98 (1H, dd), 7.79 (2H, d), 7.55 (1H,
d), 7.30 (2H, d), 7.07 (1H, d), 3.92 (3H, s), 2.66 (2H, s), 1.62 (2H, qu
i), 1.32 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 29277, 2852, 1717, 1590, 1300, 1160, 1086, 838, 766 MS m / z 350 (M ⁺ ), 319, 278, 265 (100%), 206

Example 12 Preparation of 2- (4-heptylphenyl) benzo [b] furan-5-carboxylic acid ( Compound 43 of Table 1 ) Compound 43 was prepared as described in Example 1 Step 5 using the following reagents. Prepared and purified in a similar manner as described: Compound 24 (4.2 g, 12 mmol), potassium hydroxide (1.4 g, 24 mmol) obtained as described in Example 40 Step 3. Colorless needle-like crystals were obtained. Yield: 3.7 g (92%). Transition (℃) K 200.3 SmC 255.8 Iso. ¹ H NMR DMSO-d ⁶ / δ 12.87 (1H, s), 8.25 (1H, s), 7.90 (1H, d), 7.83 (2H, d
), 7.68 (1H, d), 7.47 (1H, s), 7.34 (2H, d), 2.61 (2H, t), 1.59 (2H, qui
), 1.26 (8H, m), 0.85 (3H, t) IR (KBr) ν _max / cm ^-1 3450, 2926, 2849, 2361, 1674, 1612, 1507, 1168, 912
, 836 MS m / z 336 (M ⁺ ), 264, 251 (100%), 206, 178

Example 13 Preparation of 2- (4-heptylphenyl) benzo [b] furan-5-carboxamide (Compound 44 in Table 1 ) Compound 44 was prepared as described in Example 1 Step 6 using the following reagents. Prepared and purified in the same manner as described above: Compound 43 (Example 12) (1.0 g, 3 mmol), thionyl chloride (1.1 g, 9 mmol).
, Ammonia (d 0.880, 2.0 ml). A white solid was obtained. Yield: 0.6 g (60%), melting point: 242-243 ° C. ¹ H NMR DMSO-d ⁶ / δ 8.10 (1H, d), 7.78 (2H, d), 7.77 (1H, d), 7.54 (1H, d
), 7.28 (2H, d), 6.81 (1H, s), 5.85 (1H, s), 2.64 (2H, t), 1.63 (2H, qui)
), 1.25 (8H, m), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 3419, 3192, 2922, 1646, 1608, 1391, 912, 801 MS m / z 335 (M ⁺ ), 250 (100%), 217, 206, 178

Example 14 Preparation of Compound 54 in Table 1 (2- (4-heptylphenyl) -5-cyanobenzo [b] furan) Compound 54 was prepared from the following reagents as described in Example 1, Step 7. Prepared and purified in a similar manner: Compound 44 (Example 13) (0.6 g, 1.6 mmol), thionyl chloride (1.9 g, 16 mmol).
). Colorless crystals were obtained. Yield: 0.2 g (39%). Purity (hplc)> 99.9%. Transition (℃) K 86.5 N 87.5 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.92 (1H, d), 7.79 (2H, d), 7.61 (1H, d), 7.55 (1H, dd)
, 7.31 (2H, d), 7.05 (1H, s), 2.66 (2H, t), 1.65 (2H, qui), 1.30 (8H, m)
, 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2920, 2840, 2229, 1616, 1504, 1119, 881, 741 MS m / z 317 (M ⁺ ), 245, 232 (100%), 203, 176

Example 15 Preparation of Compound 45 of Table 1 (Methyl 2- (4 -nonyloxyphenyl ) benzo [b] furan- 5-carboxylate) 4-Nonyloxybenzoic acid in thionyl chloride (16.4 g, 138 mmol) (3.2g, 12m
(mol) suspension was stirred overnight with the moisture removed. Bring the solution to reflux (1 hour)
, Cooled. Excess thionyl chloride was removed in vacuo. Residual hydrochloric acid was removed by repeating removal of the toluene in vacuo after adding dry toluene. This acid chloride was prepared as in Example 11.
2-Hydroxy-5- (methoxycarbonyl) benzyltriphenylphosphonium chloride (4.6 g, 10 mmol) obtained as described in step 2 and dry toluene (45 m
In l) was added dry triethylamine (3.0 g, 30 mmol) and the mixture was refluxed with stirring under nitrogen (18 h). The reaction was monitored by tlc analysis. Cool the mixture,
The triethylammonium chloride precipitate was filtered and the solvent removed in vacuo. The product was purified by flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C.), dichloromethane 7: 3] and then recrystallized (hexane). A white solid was obtained. Yield: 0.9 g (22%). Transition (℃) K 151.5 SmA 152.0 Iso. (Data of Example 15)

Example 16 Preparation of 2- (4-nonyloxyphenyl) benzo [b] furan-5-carboxylic acid (Compound 46 in Table 1 ) Compound 46 was prepared from the following reagents in Example 1, Step 5 Prepared and purified in a similar manner as described: Compound 45 (0.8 g, 1.9 mmol) obtained as described in Example 15, potassium hydroxide (0.2 g, 4 mmol). A white crystalline solid was obtained. Yield: 0.6 g (86%). Transition (℃) K 172 SmC 193.2 N 253.7 Iso. ¹ H NMR CD ₂ Cl ₂ , DMSO-d ⁶ / δ 8.27 (1H, d), 7.97 (1H, dd), 7.81 (2H, d), 7.5
2 (1H, d), 7.00 (1H, d), 6.99 (2H, d), 4.02 (2H, t), 3.50 (1H, s), 1.80
(2H, t), 1.48 (2H, m), 1.27 (10H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 3450, 2920, 2857, 1679, 1615, 1504, 802, 769 MS m / z 380 (M ⁺ ), 363, 336, 254 (100%), 225

Example 17 Preparation of 2- (4-nonyloxyphenyl) benzo [b] furan-5-carboxamide ( Compound 47 of Table 1 ) Compound 47 was described in Example 1, Step 6 using the following reagents. Prepared and purified in the same manner as described above: Compound 46 (0.5 g, 1.4 mmol) obtained as described in Example 16, thionyl chloride (0.5 g, 4 mmol), ammonia (d 0.880, 1.0 ml). . A white solid was obtained. Yield: 0.2 g (38%). Transition (℃) K 225 SmC N 235 Iso. ¹ H NMR CDCl ₃ / δ 8.15 (1H, s), 7.83 (1H, d), 7.80 (2H, d), 7.62 (1H, s),
7.51 (1H, d), 6.99 (2H, d), 6.98 (1H, s), 6.53 (1H, s), 4.02 (2H, t), 1
.81 (2H, qui), 1.42 (2H, m), 1.28 (10H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 3440, 3200, 2919, 2850, 1645, 1611, 1504, 835, 807
, 770 MS m / z 379 (M ⁺ ), 350, 336, 254 (100%), 238

Example 18 Preparation of 2- (4-nonyloxyphenyl) -5-cyanobenzo [b] furan ( Compound 16 in Table 1 ) Compound 16 was prepared as described in Example 1 Step 7 using the following reagents. Prepared and purified in the same manner as described above: Compound 47 from Example 17 (0.2 g, 0.5 mmol), thionyl chloride (0.6 g, 5 mmol).
. A white solid was obtained. Yield: 0.04 g (22%). Purity (hplc)> 96.6%. Transition (℃) K 103.0 SmA 119.7 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.90 (1H, dd), 7.80 (2H, d), 7.59 (1H, d), 7.53 (1H, dd
), 7.00 (2H, d), 6.96 (1H, d), 4.02 2H, t), 1.80 (2H, qui), 1.47 (2H. M)
, 1.34-1.26 (10H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2921, 2850, 2225, 1609, 1504, 1175, 1010, 875, 802
MS m / z 361 (M ⁺ ), 235 (100%), 206, 190, 164

Example 19 Preparation Step 1 of Compound 18 in Table 1 Preparation of Benzonitrile-4-Boric Acid Benzonitrile-4-boric acid was prepared as described in Example 9, Step 4 using the following reagents. Prepared and purified by the method of: 4-bromobenzonitrile (25.0 g, 37 mmol), n-butyllithium (in hexane)
2.5M, 57.5ml, 44mmol), trimethylborate (28.5g, 274mmol). A white solid was obtained. Yield: 16.6 g (82%). MS m / z 147 (M ⁺ ), 119, 103, 91, 43 (100%)

Step 2 Preparation of 2 -heptyl-5-bromobenzo [b] furan n-Butyllithium (2.5 M in hexane, 3.3 ml, 8 mmol) was dried under nitrogen at -70 ° C. with stirring while diisopropylamine (0.9 g, 8 mmol). The system was degassed, flushed with nitrogen, and 5-bromobenzo [b] furan (in dry tetrahydrofuran (30 ml).
Example 9 step 2) (1.5 g, 7.6 mmol) was added dropwise with stirring. 2 more
After stirring for 0 minutes, n-heptyl iodide (2.6 g, 11 mmol) was added dropwise. The mixture was allowed to come to room temperature with stirring under nitrogen. It was poured into water and ether was added. The separated aqueous layer was washed with ether (2 × 50 ml), the combined organic layers were washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The residue was purified by flash chromatography [silica gel / petroleum fraction (boiling point 40-60 ° C)] and then distilled. A colorless liquid was obtained. Yield: 0.3 g (20%), Boiling point: 0.02 mmHg, 170 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.60 (1H, dd), 7.29 (1H, s), 7.28 (1H s), 6.36 (1H,
s), 2.75 (2H, t), 1.73 (2H, qui), 1.32 (8H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2861, 1600, 1165, 1051, 949, 898, 731, 671, 5
82 MS m / z 296, 294 (M ⁺ ), 239, 211 (100%), 158, 109

Step 3 Preparation of 2-heptyl-5- (4-cyanophenyl) benzo [b] furan (Compound 48 in Table 1) Compound 48 was prepared as described in Example 1, Step 4 using the following reagents. Prepared and purified in a similar manner to: Benzonitrile-4-boric acid from step 1 (0.2 g, 1.5 mmol), 2-from step 2
Heptyl-5-bromobenzo [b] furan (0.4 g, 1.4 mmol), sodium carbonate (0.4
g, 3.5 mmol), tetrakis (triethylphosphine) palladium (0) (0.05 g
, 0.04 mmol). A white solid was obtained. Yield: 0.03 g (7%). Purity (hplc) 90.5%. Transition (℃) K 43.0 (30.9 N) Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.71 (5H, m), 7.47 (1H, d), 7.43 (1H, dd), 6.45 (1H,
d), 2.77 (2H, t), 1.74 (2H, qui), 1.33 (8H, m), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 2934, 2861, 2229, 1608, 1468, 844, 808 MS m / z 317 (M ⁺ ), 274, 260, 232 (106%), 190

Example 20 Preparation Step 1 of Compound 28 in Table 1 Preparation of 1 -Bromo-4'-pentylbiphenyl Example 1 Step except that dry 1,2-dichloroethane (600 ml) was used in place of dry dichloromethane. By a method similar to that described in 1, 4-bromobiphenyl (35.0 g, 150 mmol), valeryl chloride (21.8 g, 181 mmol), ammonium chloride (22.0 g, 164 mmol), poly (methylhydrosiloxane) (24.0 g, 399 mmol) was reacted. The title product was recrystallized from ethanol. A light brown solid was obtained. Yield: 21.1g (46%), Melting point: 94-96 ℃ (lit. [Jawdosiuk, 1977 # 157] 95-96 ℃)
. ¹ H NMR CD ₂ Cl ₂ / δ 7.56 (2H, d), 7.49 (2H, d), 7.48 (2H, d), 7.27 (2H, d)
, 2.64 (2H, t), 2.64 (2H, t), 1.65 (2H, qui), 1.36 (4H, m), 0.90 (3H, t)
IR (KBr) ν _max / cm ^-1 2931, 2865, 1690, 1137, 1079, 803, 502 MS m / z 304, 302 (M ⁺ ), 247 (100%) 165, 152, 139

Step 2 Preparation of 4'- Pentylbiphenylboric acid n-Butyllithium (2.5M in hexane, 231 ml, 577 mmol) in nitrogen at -70 ° C in dry tetrahydrofuran (90 ml) A stirred solution of the product of step 1 Was added drop by drop. Stirring under nitrogen was continued (30 min) and trimethylborate (6.9 g, 66 mmol) was added dropwise maintaining the temperature below -10 ° C. The system was allowed to come to room temperature with stirring under nitrogen. Hydrochloric acid (5M, 14ml) was added with stirring. The mixture was poured into water and ether was added. The separated aqueous layer was washed with ether (2 × 200 ml), the combined organic layers were washed with water and brine, dried (MgSO ₄ ) and the solvent removed in vacuo. A light brown solid was obtained. Yield: 7.2 g (81%). MS m / z 268 (M ⁺ ), 224, 183 (100%), 167, 152

Step 3 2-Cyano-5- (4'-pentylphenyl) benzo [b] furan (Compound 28 in Table 1
)) 2-Cyano-5-bromobenzo [b] furan (0.6 g, 2.7 mmol) obtained as described in Example 2, Step 3 in 1,2-dimethoxyethane (5 ml) and sodium carbonate (0.7 g). ，
6.8 mmol) was stirred under nitrogen. Tetrakis (triethylphosphine) palladium (0) (0.3 g, 0.3 mmol) was added followed by the product of step 2 (1.1 g, 4.1 mmol) in 1,2-dimethoxyethane (10 ml) and the mixture was stirred under nitrogen. While heating (80 ℃)
Yes (4 hours). glc and tlc analysis showed the reaction was complete. After cooling, the reaction mixture was poured into water and ether was added. Separated aqueous layer with ether (2 x 100 ml)
In washing, and the combined organic layers were washed with water and brine, dried (MgSO _4). After removing the solvent in vacuo, the residue was purified by flash chromatography [silica gel / petroleum fraction (boiling point 40-60 ° C) (impure); petroleum fraction (boiling point 40-60 ° C), dichloromethane 7: 3 ( Product)]. The desired product was recrystallized (hexane). Colorless needle-like crystals were obtained. Yield: 0.1 g (10%). Purity (hplc) 99.9%. Transition (℃) K 134.0 B 147.3 N 255.6 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.94 (1H, dd), 7.82 (1H, dd), 7.71 (2H, d), 7.69 (2H,
d), 7.66 (1H, ddd), 7.58 (2H, d), 7.57 (1H, d), 7.29 (2H, d), 2.66 (2H,
t), 1.66 (2H, qui), 1.36 (4H, m), 0.92 (3H, t) IR (KBr) ν _max / cm ^-1 2931, 2862, 2237, 1505, 1179, 949, 805 MS m / z 365 (M ⁺ ), (100%), 346, 308, 252, 58

Example 21 Preparation Step 1 of Compound 29 in Table 1 Preparation of 2- (4'-pentylbiphenyl) -5-cyanobenzo [b] furan Compound 29 was prepared in Example 1 Step 4 using the following reagents. Prepared and purified in a similar manner as described: 1-Bromo-4'-pentylbiphenyl (Example 20 step 1) (1.5 g, 5 mmol), 5
-Cyanobenzo [b] furan-2-borate (Example 9, Step 4) (1.5 g, 8 mmol), sodium carbonate (1.3 g, 13 mmol), tetrakis (triethylphosphine) palladium (0) (0.6 g, 0.6 mmol) . The product was recrystallized from ethanol / dichloromethane 5: 1. A white crystalline solid was obtained. Yield: 0.3 g (16%). Purity (hplc)> 99%. Transition (℃) K 187.1 N 284.2 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.96 (1H, d), 7.95 (2H, d), 7.73 (2H, d), 7.63 (1H,
d), 7.58 (2H, d), 7.56 (1H, dd), 7.30 (2H, d), 7.13 (1H, d), 2.66 (2H, t
), 1.66 (2H, qui), 1.36 (4H, m), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2859, 2229, 1497, 1122, 913, 803, 746 MS m / z 365 (M ⁺ ), 308, 277, 165, 43 (100%)

Example 22 Preparation Step 1 of Compound 49 in Table 1 Preparation of 5-bromobenzo [b] furan-2-boric acid Dry diisopropylamine (2.0 g, 20 mmol) was added to n-butyllithium (-10 ° C).
2.5M in hexanes, 8 ml, 20 mmol) and the mixture was stirred under nitrogen (20 min).
5-Bromobenzo [obtained as described in Example 9, Step 2, in dry ether (35 ml).
b] Furan (3.5 g, 18 mmol) was added and the mixture was stirred at -10 ° C under nitrogen (2 h).
). Trimethylborate (3.7 g, 36 mmol) was added while keeping the temperature low and the mixture was allowed to warm to room temperature with stirring under nitrogen. Hydrochloric acid (5M, 15mmol) was added with stirring. The mixture was poured into water and ether was added. The separated aqueous layer was washed with ether (
2 x 50 ml) and the combined organic layers were washed with sodium hydroxide solution (10%, 30 ml). The separated aqueous layer was washed with light oil (40 to 60 ° C. distillate) and acidified to pH 3 with hydrochloric acid (5M). It was washed with ether (2 x 50 ml). The combined organic layers were washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. A pale orange solid was obtained. Yield: 3.4 g (78%). ¹ H NMR DMSO-d ⁶ / δ 8.62 (2H, s), 7.92 (1H, d), 7.56 (1H, d), 7.46 (1H, d
d), 7.42 (1H, s) MS m / z 196 (M ⁺ -B (OH) ₂ ), 165, 151, 117, 89 (100%),

Step 2 Preparation of 1-Iodo-4-pentylbenzene 1-Iodo-4-pentylbenzene was prepared and purified in the same manner as described in Example 1, Step 1 using the following reagents: Iodobenzene (20.4g, 100mmol), valeryl chloride (14.5g, 120mmol), ammonium chloride (14.7g, 110mmol), poly (methylhydrosiloxane) (16.0g, 267mm)
ol). A pale yellow liquid was obtained. Yield: 14.4g (53%), Boiling point: 0.01mmHg, 105 ° C. ¹ H NMR CDCl ₃ / δ 7.58 (2H, d), 6.93 (2H, d), 2.54 (2H, t), 1.58 (2H, m),
1.31 (4H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2962, 2862, 1486, 1118, 1065, 825, 795 MS m / z 274 (M ⁺ ), 217 (100% ), 203, 175, 89

Step 3 Preparation of 2- (4-pentylphenyl) -5-bromobenzo [b] furan (Compound 49 in Table 1) Compound 49 was prepared as described in Example 1, Step 4, using the following reagents. Prepared and purified in a similar manner: 1-iodo-4-pentylbenzene from step 2 (3 g, 11 mmol), 5-from step 1
Bromobenzo [b] furan-2-boric acid (1.3 g, 5 mmol), sodium carbonate (1.4 g, 1
3.5 mmol), tetrakis (triethylphosphine) palladium (0) (0.3 g, 0.1
3 mmol). The product was recrystallized from hexane. A white crystalline solid was obtained. Yield: 0.3 g (16%), melting point: 147-150 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.765 (2H, d), 7.71 (1H, dd), 7.41 (1H, d), 7.36 (1H,
dd), 7.28 (2H, d), 6.96 (1H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.34 (4H
, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2932, 2860, 1610, 1583, 1162, 873, 795, 670, 508 MS m / z 344, 342 (M ⁺ ), 287 (100%), 274, 206, 152

[0129] Compound 50 (2- (4-pentylphenyl) -5- (4'-cyanophenyl) Ben zo [b] furan Preparation Compound 50 of Example 23 in Table 1, Example using the following reagents Prepared and purified by a method similar to that described in 1 Step 4: Compound 49 (Example 22) (0.3 g, 0.9 mmol), benzonitrile-4-boric acid (Example 19 Step 1) (0.2 g, 1.0 mmol), sodium carbonate (0.2 g, 2 mmol), tetrakis (triethylphosphine) palladium (0) (0.03 g, 0.03 mmol) The product was flash chromatographed [silica gel / hexane, propionitrile 40: 1], then Purification by recrystallization (ethanol) gave a white crystalline solid Yield: 0.04 g (12%) Purity (hplc) 98% Transition (° C) K 133.8 N 230.5 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.74 1H, d), 7.73 (2H, d), 7.68 (4H, s), 7.53 (1H, d
), 7.45 (1H, dd), 7.23 (2H, d), 6.99 (1H, d), 2.58 (2H, t), 1.58 (2H, qu
i), 1.27 (4H, m), 0.83 (3H, t) IR (KBr) ν _max / cm ^-1 2927, 2854, 2226, 1607, 1463, 1153, 1125, 889, 841
, 813 MS m / z 365 (M ⁺ ), 308 (100%), 264, 176, 154

Example 24 Preparation Step 1 of Compound 35 in Table 1 Preparation of 5- (4-pentylphenyl) benzo [b] furan 5- (4-pentylphenyl) benzo [b] furan was prepared from the following reagents. Prepared and purified by a method similar to that described in Example 1, Step 4: 5-Bromobenzo [b] furan (Example 9, Step 2) (2.5 g, 13 mmol), 4-pentylbenzeneboronic acid (Example 3). Step 2) (2.9 g, 15 mmol), sodium carbonate (3.5 g,
33mmol), tetrakis (triethylphosphine) palladium (0) (0.5g, 0.5m
mol). Flash chromatography of the product [silica gel / petroleum fraction (boiling point 40-60 ° C
)], Followed by recrystallization (hexane). Colorless plate-like crystals were obtained. Yield: 1.2 g (35%), melting point: 62-64 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.54 (2H, d), 7.53 (1H, d), 7.52 (1H, dd), 7.27 (2H, d
), 6.84 (1H, dd), 2.65 (2H, t), 1.66 (2H, qui), 1.36 (4H, m), 0.91 (3H,
t) IR (KBr) ν _max / cm ^-1 2958, 2931, 2858, 1516, 1131, 885, 845, 806, 771, 7
43 MS m / z 264 (M ⁺ ), 207 (100%), 178, 165, 152

Step 2 Preparation of 5- (4-pentylphenyl) benzo [b] furan-2-boric acid 5- (4-Pentylphenyl) benzo [b] furan-2-boric acid was prepared from the following reagents.
Prepared and purified by a method similar to that described in Example 20, Step 2: 5- (4-pentylphenyl) benzo [b] furan (1.2 g, 5 mmol), n-butyllithium (2.5 in hexane). M, 2 ml, 5 mmol), trimethylborate (0.9 g,
9 mmol). A pale pink solid was obtained. Yield: 1.2 g (84%). MS m / z 264 (M ⁺ -B (OH) ₂ ), 207 (100%), 177, 151, 127

Step 3 Preparation of 2- (4-Cyanophenyl) -5- (4'-pentylphenyl) benzo [b] furan ( Compound 35 in Table 1 ) Compound 35 was prepared from the following reagents from Example 20 step Prepared and purified in a similar manner as described in 3. Benzonitrile-4-boric acid (Example 19 step 1) (0.7 g, 4 mmol), step 2 above.
(1.1 g, 4 mmol), sodium carbonate (1.1 g, 10 mmol), tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol). The product was recrystallized from carbon tetrachloride. Colorless orthorhombic crystals were obtained. Yield: 0.4 g (30%). Purity (hplc) 99.9%. Transition (℃) K 139.0 N 252.6 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.99 (2H, d), 7.83 (1H, dd), 7.76 (2H, d), 7.62-7.57
(2H, m), 7.55 (2H, d), 7.29 (2H, d), 7.27 (2H, d), 2.66 (2H, t), 1.66 (2
H, qui), 1.38-1.34 (4H, m), 0.92 (3H, t) IR (KBr) ν _max / cm ^-1 2968, 2854, 2224, 1607, 1155, 842, 802 MS m / z 365 (M ⁺ ), 308 (100%), 277, 252, 154

Example 25 Preparation Step 1 of Compound 51 in Table 1 Preparation of 2- (4-pentylphenoxy) acetaldehyde dimethyl acetal 2- (4-Pentylphenoxy) acetaldehyde dimethyl acetal was prepared using the following reagents in Example 8 Prepared and purified by a method similar to that described in step 1: 4-pentylphenol (9.9 g, 60 mmol), bromoacetaldehyde dimethyl acetal (12.4 g, 73 mmol), potassium carbonate (20.8 g, 151 mmol), potassium iodide. (0.6 g, 4 mmol). A pale yellow liquid was obtained. Yield: 4.8g (32%), Boiling point: 0.01mmHg at 125 ℃. ¹ H NMR CD ₂ Cl ₂ / δ 7.08 (2H, d), 6.84 (2H, d), 4.72 (1H, t), 3.99 (2H, t)
, 3.46 (6H, s), 2.53 (2H, t), 1.57 (2H, qui), 1.31 (4H, m), 0.88 (3H, t)
IR (KBr) ν _max / cm ^-1 2936, 1616, 1514, 1247, 1139, 1081, 976, 827,757
MS m / z 252 (M ⁺ ), 221, 149, 107, 75 (100%)

Step 2 Preparation of 5-Pentylbenzo [b] furan 5-Pentylbenzo [b] furan was prepared and purified from the following reagents in a similar manner as described in Example 8, Step 2: The product of step 1 (4.8 g, 19 mmol), polyphosphoric acid (4.6 g). A colorless liquid was obtained. Yield: 2.2g (62%), Boiling point: 0.1mmHg at 125 ℃. ¹ H NMR CD ₂ Cl ₂ / δ 7.61 (1H, d), 7.41 (1H, s), 7.40 (1H d), 7.13 (1H, dd),
6.74 (1H, dd), 2.70 (2H, t), 1.65 (2H, qui), 1.35 (4H, m), 0.91 (3H, t)
IR (KBr) ν _max / cm ^-1 2934, 2861, 1468, 1198, 1033, 881, 812, 764, 734 MS m / z 188 (M ⁺ ), 145, 131 (100%), 115, 91

Step 3 Preparation of 5-pentylbenzo [b] furan-2-boric acid The product of Step 2 (2.2 g, 12 mmol), n-butyllithium (2.5 M in hexanes, 5.2
ml, 13 mmol), trimethylborate (2.59 g, 24 mmol) were reacted in a similar manner as described in Example 20, step 2, to give the title compound. A pale orange solid was obtained. Yield: 2.7 g (97%). MS m / z 232 (M ⁺ ), 187, 174, 146, 130 (100%)

Step 4 Preparation of 4 -Cyano-4′-iodobiphenyl 4 -Cyano-4′-iodobuphenyl was prepared and purified from the following reagents by a method similar to that described in Example 1, Step 4. Was done: p-diiodobenzene (14.7 g, 44 mmol), benzonitrile-4-boric acid (Example 1
9 step 1) (5.0 g, 34 mmol), sodium carbonate (21.6 g, 204 mmol), tetrakis (triethylphosphine) palladium (0) (0.3 g, 0.3 mmol). The product was recrystallized from ethanol. A white crystalline product was obtained. Yield: 1.0 g (10%), melting point: 174-176 ° C (lit. [Pummerer, 1931 # 158] 166 ° C)
. ¹ H NMR CD ₂ Cl ₂ / δ 7.83 (2H, d), 7.74 (2H, d), 7.68 (2H, d), 7.37 (2H, d) IR (KBr) ν _max / cm ^-1 2227, 1604, 1477, 997, 853, 813, 561 MS m / z 305 (M ⁺ ), (100%), 178, 151, 127, 75

Step 5 2- (4'-Cyanobiphenyl) -5-pentylbenzo [b] furan (Compound 5 in Table 1
The compound 51 prepared in 1) was prepared using the product of the above step 4 (1.0 g, 3 mmol) and the product of the above step 3 (0
.8 g, 4 mmol), sodium carbonate (0.9 g, 8 mmol) and tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol) prepared and purified in a similar manner as described in Example 20, step 3. did. The product was recrystallized from ethanol. Colorless plate-like crystals were obtained. Yield: 36 mg (2%). Purity (hplc) 99.5%. Transition (℃) K 150.8 B 167.0 N 280.3 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.97 (2H, d), 7.79-7.75 (4H, m), 7.72 (2H, d), 7.44 (
1H, d), 7.42 (1H, d), 7.15 (1H, dd), 7.09 (1H, d), 2.71 (2H, t), 1.67 (2
H, qui), 1.38-1.33 (4H, m), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 2927, 2858, 2229, 1603, 1493, 1465, 1189, 825, 802 MS m / z 365 (M ⁺ ), 322, 308 (100%), 264, 154

Example 26 Preparation Step 1 of Compound 52 in Table 1 Preparation of 2-Pentyl-5-bromobenzo [b] furan 2-Pentyl-5-bromobenzo [b] furan was prepared in Example 19 using the following reagents.
Prepared and purified in a similar manner as described in Step 2: 5-Bromobenzo [b] furan (Example 9 Step 2) (12.0 g, 61 mmol), dry diisopropylamine (6.8 g, 67 mmol), n-butyl. Lithium (2.5M in hexane, 26.8m
l, 67 mmol), n-pentyl iodide (24.2 g, 122 mmol). A colorless liquid was obtained. Yield: 2.6 g (16%), Boiling point: 0.6 mmHg at 198 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.61 (1H, dd), 7.30 (1H, d), 7.28 (1H, d), 6.36 (1H, s
), 2.76 (2H, dt), 1.74 (2H, d), 1.37 (4H, m), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 2935, 2868, 1599, 1450, 1117, 1050 , 948, 867, 671,
579 MS m / z 268,266 (M ⁺ ), 251, 223, 208 (100%), 116

Step 2 Preparation of 5-pentylbenzo [b] furan-5-boric acid The title compound is the product of Step 1 (2.5 g, 9 mmol), magnesium (0.3 g, 11 m
mol) and trimethylborate (2.09 g, 19 mmol) and prepared and purified in a similar manner as described in Example 1, Step 2: A pale yellow solid was obtained. Yield: 1.7 g (78%). MS m / z 642 (3M ⁺ -3H ₂ O), 585, 255, 188, 131 (100%)

Step 3 Preparation of 2-Pentyl-5- (4- (4′-cyano) biphenyl) benzo [b] furan (Compound 52 in Table 1 ) Compound 52 was prepared as described in Example 1, Step 4. In the same amount as above, the product of Step 3 above (1.7 g, 7 mmol), 4-cyano-4′-iodobiphenyl (Example 25 Step 2) (
Prepared and purified from 1.7 g, 6 mmol), sodium carbonate (1.5 g, 14 mmol), and tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol). The reaction was carried out with exclusion of light. A white crystalline solid was obtained. Yield: 0.1 g (5%). Purity (hplc) 97.6%. Transition (℃) K 94.8 N 236.7 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.77-7.68 (9H, m), 7.48 (1H, dd), 7.47 (1H, d), 6.45
(1H, s), 2.78 (2H, t), 1.76 (2H, qui), 1.40-1.34 (4H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2935, 2860, 2228 , 1604, 1466, 1120, 948, 829, 802 MS m / z 365 (M ⁺ ), 350, 322, 308 (100%), 278

Example 27 Preparation Step 1 of Compound 53 in Table 1 Preparation of Benzo [b] furan-5-boric Acid Benzo [b] furan-5-boric acid was prepared from 5-bromobenzo [b] furan (Example 9). Step 2) was prepared and purified from (2.0 g, 10 mmol), magnesium (0.3 g, 12 mmol) and trimethylborate (2.1 g, 20 mmol) in a similar manner as described in Example 1, step 2. A light brown solid was obtained. Yield: 0.7 g (43%). MS m / z 432 (3M ⁺ -3H ₂ O), 144 (100%), 117, 89, 63

Step 2 4- (4'-pentylcyclohexyl) phenyl trifluoromethanesulfonate
Preparation of trifluoromethanesulfonic anhydride (6.5g, 23mmmol), dried pyridine (80m
l) 4- (trans-n-yentylcyclohexyl) phenol (5.0 g,
20 mmol) to a stirred cooled (0 ° C.) solution was added dropwise under nitrogen. The mixture was stirred overnight at room temperature. It was poured into water and ether was added. The separated aqueous layer was washed with ether (2 x 100 ml). The combined organic layer was washed with water, hydrochloric acid (10%) (2 times), and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The product was purified by flash chromatography [silica gel / petroleum fraction (boiling point 40-60 ° C), dichloromethane 7: 3]. A pale yellow oil was obtained. Yield: 5.2 g (69%). ¹ H NMR CD ₂ Cl ₂ / δ 7.21 (2H, d), 7.10 (2H, d), 2.44 (1H, tt), 1.82-1.81 (2
H, m), 1.78-1.77 (2H, m), 1.38- 1.36 (1H, m), 1.34-1.31 (1H, m), 1.26-1
.12 (9H, m), 1.02-0.99 (1H, m), 0.96-0.93 (1H, m), 0.81 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2858, 1503, 1427, 1143, 1018, 837, 740, 607 MS m / z 378 (M ⁺ ), 307, 252, 175, 69 (100%)

Step 3 Preparation of 5- (4'-pentylcyclohexyl-4-phenyl) benzo [b] furan 5- (4'-pentylcyclohexyl-4-phenyl) benzo [b] furan, compound of formula (IXA) Was prepared and purified in the same manner as described in Example 1, Step 4, from the following reagents: product of Step 2 above (3.4 g, 9 mmol), product of Step 1 above (1.6 g, 10 mmol). ),
Sodium carbonate (2.4 g, 23 mmol), tetrakis (triethylphosphine) palladium (0) (0.3 g, 0.3 mmol). Volatiles were removed by heating in vacuum (95 ° C.) (12 hours). A white solid was obtained. Yield: 1.9 g (61%). Transition (℃) K 116.3 N 153.7 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.80-7.79 (1H, m), 7.67 (1H, d), 7.56-7.51 (4H, m), 7.3
0 (2H, d), 6.84 (1H, dd), 2.53 (1H, tt), 1.94-1.88 (4H, m), 1.48 (2H, dd
d), 1.35-1.22 (9H, m), 1.08 (2H, ddd), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 3124, 2924, 2853, 1463, 1131, 1027, 883, 742 , 697 MS m / z 346 (M ⁺ ), 331, 303, 275, 233 (100%)

Step 4 5- (4'-Pentylcyclohexyl-4-phenyl) benzo [b] furan-2-carbo
Preparation of Acid (Compound 53) Compound 53 was prepared from Step 3 of Example 8 from the product of Step 3 (1.9 g, 5.5 mmol) and n-butyllithium (2.5 M in hexane, 2.4 ml, 6.1 mmol). Prepared and purified in a similar manner as described. A white solid was obtained. Yield: 2.0 g (79%). Transition (℃) K 183 N 299 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.79 (1H, dd), 7.59 (1H, dd), 7.54 (1H, d), 7.47 (2H, d
), 7.45 (1H, d), 7.23 (2H, d), 2.45-2.42 (1H m), 1.85-1.80 (4H, m), 1.43
(2H.ddd), 1.27-1.13 (9H, m), 1.00 (2H, ddd), 0.82 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2853, 1691, 1566, 1173, 813 MS m / z 390 (M ⁺ ), (100%), 346, 333, 264, 189

Example 28 Preparation of compound 54 in Table 1 (5- (4'-pentylcyclohexyl-4-phenyl) benzo [b ] furan-2-carboxamide) Compound 54 was prepared using the following reagents. Prepared and purified in a manner similar to that described in Step 1. Compound 53 (Example 27) (2.0 g, 4.3 mmol), thionyl chloride (1.5 g, 13 mmol)
, Ammonia (d 0.880, 2.9 ml). Fibrous white needle-like crystals were obtained. Yield: 1.1 g (66%). Transition (℃) K 275 N 296 Iso. ¹ H NMR CD ₂ Cl ₂ / δ, DMSO-d ⁶ / δ 7.83 (1H, d), 7.63 (1H, dd), 7.56 (1H, d),
7.53 (2H, d), 7.46 1H d), 6.92 (1H s), 6.54 (1H, s), 2.42-2.35 (1H, m),
1.91-1.85 (4H, m), 1.47 (2H, ddd), 1.32-1.20 (9H, m), 1.05 (2H, ddd), 0.
88 (3H, t) IR (KBr) ν _max / cm ^-1 3393, 3170, 2928, 2852, 1675, 1615, 1168, 817 MS m / z 389 (M ⁺ ), 316, 301, 250, 58 (100 %)

Example 29 2-Cyano-5- (4'-trans-pentylcyclohexyl-4-phenyl) benzo [
b] Preparation of Furan (Compound 54 in Table 1) Compound 54 was prepared as described in Example 1, Step 7, from compound 54 (Example 28) (1.0 g, 2.6 mmol) and thionyl chloride (3.2 g, 26 mmol). Prepared and purified in the same manner as in. The product was recrystallized from ethanol. Yield: 0.5 g (52%). Purity (hplc)> 99%. Transition (℃) K 113.0 N 240.7 Iso. ¹ H NMR CD ₂ Cl ₂ / δ 7.86 (1H dd), 7.75 (1H, dd), 7.61 (1H, dt), 7.55 (1H, d
), 7.54 (2H, d), 7.32 (2H, d), 2.53 (1H, tt), 1.93-1.87 (4H, m), 1.56-1.
44 (4H, m), 1.35-1.19 (7H, m), 1.08 (2H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2925, 2854, 2234, 1558, 1515, 1462 , 1178, 1128, 950
, 887 MS m / z 371 (M ⁺ ) (100%), 300, 245, 232, 189

Example 30 Preparation step of compound 56 in Table 1 Preparation of ethyl 5-methoxybenzo [b] furan-2-carboxylate Ethyl 5-methoxybenzo [b] furan-2-carboxylate is 5-methoxy Salicylaldehyde (20.0g, 131mmol), diethyl bromomalonate (26.3g, 1
10 mmol), potassium carbonate (32.5 g, 236 mmol), potassium iodide (0.9 g, 0.9 mmol)
) Was prepared and purified by a method similar to that described in Example 1, step 3. Colorless cubic crystals were obtained. Yield: 14.5 g (50%), melting point: 58-59.5 ° C, boiling point: 0.02 mmHg, 150 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.47 (1H, ddd), 7.45 (1H, d), 7.09 (1H, d), 7.06 (1H, dd
), 4.39 (2H, q), 3.83 (3H, s), 1.40 (3H, t) IR (KBr) ν _max / cm ^-1 29882 1721, 1560, 11957 940, 846, 822 MS m / z 220 (M ⁺ ), (100%), 205, 192, 175, 119

Step 2 Preparation of 5-methoxybenzo [b] furan-2-carboxylic acid The title compound is the product of Step 1 (14.5 g, 66 mmol) and potassium hydroxide (7.3 g).
, 130 mmol) in the same manner as described in Example 1, step 5.
Colorless crystals were obtained. Yield: 6.1 g (48%). Transition (℃) K 208 N 221 Iso. ¹ H NMR CD ₂ Cl ₂ , DMSO-d ⁶ / δ 11.5 (1H s), 7.41 (1H, d), 7.38 (1H, d), 7.06
(1h, d), 7.00 (1H, dd), 3.78 (3H, s) IR (KBr) ν _max / cm ^-1 2953, 1689, 1566, 1160, 943, 898, 850, 797 MS m / z (192 ⁺ ) (100%), 177, 162, 149, 107

Step 3 Preparation of 5-Methoxybenzo [b] furan-2-carboxamide The title compound is the product of Step 2 (6.0 g, 31 mmol), thionyl chloride (11.0 g, 9 mmol).
3 mmol) and ammonia (d 0.880, 11.0 ml) and prepared and purified in a similar manner as described in Example 1, step 6. Colorless plate-like crystals were obtained. Yield: 4.6 g (78%). ¹ H NMR CD ₂ Cl ₂ / δ 7.42 (2H, d), 7.40 (1H, s), 7.11, (1H, d), 7.04 (1H, dd)
, 6.53 (1H, s, br), 5.94 (1H, s, br), 3.84 (3H, s) IR (KBr) ν _max / cm ^-1 3451, 3138, 1692, 1608, 1476, 1156, 854, 833 MS m / z 191 (M ⁺ ) (100%), 175, 159, 148, 133

Step 4 Preparation of 2-Cyano-5-methoxybenzo [b] furan The product of Step 3 (4.8 g, 25 mmol) was prepared in the same manner as described in Example 1, Step 7.
And thionyl chloride (14.3 g, 120 mmol) were converted to the title compound. The product was recrystallized from methanol. White needle-like crystals were obtained. Yield: 1.5 g (36%), melting point: 79.5-80 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.46 (1H, ddd), 7.44 (1H, dd), 7.12 (1H, dd), 7.09 (1H,
d), 3.84 (3H, s) IR (KBr) ν _max / cm ^-1 2949, 2842, 2231, 1596, 1475, 1211, 1185, 949,877, 7
50 MS m / z 173 (M ⁺ ), (100%), 158, 130, 102, 75

Step 5 Preparation of 2-Cyano-5-hydroxybenzo [b] furan A mixture of the product of Step 4 (0.7 g, 4 mmol) and pyridinium chloride (4.6 g, 40 mmol) was refluxed (3 min). The reaction mixture was poured into ice / water. The product was extracted into ether (2 × 200 ml), the combined organic extracts were washed with water and brine, dried (M).
MgSO _4), was eliminated in vacuo the solvent. The product was recrystallized from ethanol.
Colorless crystals were obtained. Yield: 0.5 g (80%).

Step 6 2-Cyanobenzo [b] furan-5-trans- (oxycarbonyl-4-pentyloxy
Chlorohexane) (Compound 56 in Table 1) Preparation 5 Product (0.5 g, 3 mmol) and trans-4-pentylcyclohexylcarboxylic acid (0.6 g, 3 mmol) were dissolved in dry dichloromethane (30 ml), -N, N'-
Dimethylamino) pyridine (0.1 g, 1 mmol) was added and the mixture was stirred. N, N
'-Dicyclohexylcarbodiimide (0.6 g, 3 mmol) was added and stirring was continued (
24hours). The reaction was monitored by tlc analysis. The precipitate of N, N'-dicyclohexylurea was filtered and the solvent was removed in vacuo. The product was purified by flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C.), dichloromethane 7: 3] and then recrystallization (ethanol). A white crystalline solid was obtained.

Example 31 Preparation Step 1 of Compound 100 in Table 2 Preparation of 4-Bromo (2,2-dimethoxy) ethylsulfanyl benzene Sodium (13.8g, 600m) in ultra dry ethanol (400ml) with stirring under nitrogen.
mol) was added. 4-Bromothiophenol (Compound 102) (103.3g, 546mmol)
Was added and stirring was continued (5 minutes). Bromoacetaldehyde dimethyl acetal (120.0 g, 709 mmol) was added and the mixture was refluxed overnight under nitrogen with stirring. The mixture was washed with dichloromethane (3 x 100 ml). The mixture washed was washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The residue was purified by distillation. A colorless oil was obtained. Yield: 104.3g (69%), Boiling point: 2mmHg, 132 ° C. ¹ H NMR CDCl ₃ / δ 7.39 (2H, d), 7.24 (2H, d), 4.5 (1H, t), 3.36 (6H, s), 3
.08 (2H, d) IR (KBr) ν _max / cm ^-1 2930, 2830, 1470, 1120, 1090, 800, 480 MS m / z 278, 276 (M ⁺ ), 247, 215, 201, 189, 75 (100%)

Step 2 Preparation of 5-bromobenzo [b] thiophene The product of step 1 (104.3 g, 376 mmol) and polyphosphoric acid (156.2 g) were converted to 5-bromobenzo [b] thiophene in step 2 of Example 8. . A white crystalline solid was obtained. Yield: 12.0 g (15%), melting point: 46-47 ° C (lit ⁴ 47-48 ° C). ¹ H NMR CD ₂ Cl ₂ / δ 7.98 (1H, d), 7.77 (1H, d) 5 7.52 (1H, d), 7.44 (1H, dd
), 7.30 (1H, dd) IR (KBr) ν _max / cm ^-1 3080, 1576, 1399, 898, 807, 472 MS m / z 214,212 (M ⁺ ), 133 (100%), 106, 89, 81

Step 3 Preparation of 5- (4-heptylphenyl) benzo [b] thiophene Product of step 2 (4.6 g, 22 mmol) 4-heptylbenzeneboric acid (Example 1 step 2) (5.7 g, 26 mmol) ), Sodium carbonate (5.8 g, 55 mmol) and tetrakis (triethylphosphine) palladium (0) (0.8 g, 0.7 mmol) in Example 1, Step 4.
Work up as described in to give the title compound. A colorless product was obtained which solidified on cooling. Yield: 4.8g (71%), Boiling point: 0.01mmHg, 225 ℃. . ¹ H NMR CD ₂ Cl ₂ / δ 7.95 (1H, d), 7.85 (1H, d), 7.51 (1H, dd), 7.50 (2H, d),
7.42 (1H, d), 7.31 (1H, dd), 7.20 (2H, d), 2.57 (2H, t), 1.57 (2H, qui)
, 1.28-1.20 (8H, m), 0.81 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2857, 1496, 1089, 899, 805, 757 MS m / z 308 (M ⁺ ), 252,223 (100%), 167, 58

Step 4 Preparation of 5- (4-heptylphenyl) benzo [b] thiophene-2-carboxylic acid (Compound 100 of Table 2 ) Compound 100 was prepared as described in Example 8 Step 3 using the following reagents. Prepared and purified in the same manner as described above: product of step 3 above (2.5 g, 8 mmol) and n-butyllithium (2.5 M in hexane, 3
.4 ml, 9 mmol). A white solid was obtained. Yield: 1.1 g (39%), melting point: 164-170 ° C. ¹ H NMR CD ₂ Cl ₂ / δ, DMSO-d ⁶ / δ 8.05 (1H, d), 8.02 (1H, s), 7.90 (1H, d), 7
.68 (1H, dd), 7.55 (2H, d), 7.26 (2H, d), 2.63 (2H, t), 1.62 (2H, qui),
1.32-1.23 (8H, m), 0.86 (3H, t) (No acidic proton signal was observed) IR (KBr) ν _max / cm ^-1 3010, 2931, 2855, 1690, 1547, 15145, 1165, 803 , 757
, 700 MS m / z 352 (M ⁺ ), 281, 267 (100%), 221, 208

Example 32 Preparation of 5- (4-heptylphenyl) benzo [b] thiophene-2-carboxamide ( Compound 101 in Table 2 ) Compound 101 was prepared from compound 57 (Example 31) (1.1 g, 3 mmol). Thionyl chloride (1
.9 mmol) and ammonia (d 0.880, 1.1 ml) and prepared and purified in a similar manner as described in Example 1, step 6. A white crystalline solid was obtained. Yield: 1.8 g (92%), melting point: 204-205 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 8.06 (1H d,), 7.93 (1H, d), 7.81 (1H, s), 7.70 (1H, dd)
, 7.58 (2H, d), 7.30 (2H, d), 2.66 (2H, t), 1.65 (2H, qui), 1.36-1.26 (8
H, m), 0.89 (3H, t) (no H-bonded proton signal was observed) IR (KBr) ν _max / cm ^-1 3399, 3187, 2927, 2855, 1643, 1609, 1512, 1172, 800 MS m / z 351 (M ⁺ ), 279, 266 (l 00%), 248, 221

Example 33 Preparation of 2-Cyano-5- (4-heptylphenyl) benzo [b] thiophene ( Compound 102 in Table 2) Compound 102 was prepared in the same manner as described in Example 1, Step 7. In, was prepared and purified from compound 61 (Example 31) (1.0 g, 3 mmol), thionyl chloride (3.3,28 mmol). A white crystalline solid was obtained. Yield: 0.4 g (43%), melting point: 93.2 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 8.1 (1H, d), 7.97 (1H, d), 7.94 (1H, d), 7.80 (1H, dd), 7.57 (2H, d), 7.31 (2H, d) , 2.66 (2H, t), 1.65 (2H, qui), 1.35-1.30 (8H, m), 0.89 (3K t)

[0159] Example 34 4-heptyl-phenyl 5- (4-heptyl) benzo [b] furan-2-Kishireto during the preparation of dry diethyl ether preparation step 1 4-heptyl phenol (Compound 5 of Table 1) ( 100 ml of 4-heptylbenzeneboric acid (15.8 g, 72.
Hydrogen peroxide (100 vol, 387 ml, 3.39 mol) was slowly added to a stirred solution of (0 mmol) and the mixture was refluxed (2 hours). After cooling, the mixture was washed with ether (3 x 150 ml). The mixed ether layer was washed with saturated sodium sulfite solution and shaken with aqueous sodium hydroxide solution (2M). The white precipitate is filtered and the petroleum fraction (boiling point 40 ~
It was washed with 60 ° C.) and adjusted to pH 3 with hydrochloric acid (concentrated). The product is ether (3 x 150 m
l). The combined organic layers were washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The residue was purified by distillation. A colorless liquid was obtained. Yield: 4.4 g (32%), Boiling point: 0.03 mmHg, 115 ° C (lit ¹ 65 ° C) ¹ H NMR CDCl ₃ / δ 7.02 (2H, d), 6.76 (2H5, d), 5.10 (1H, s ), 2.53 (2H, d) 1. 56 (2H, m), 1. 31 (8H, m), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 3340, 2925, 1615, 1515, 1175, 830, 760 MS m / z 192 (M ⁺ ) 120, 107, 91, 43 (100%)

Step 2 Preparation of Compound 5 in Table 1 5- (4-heptylphenyl) benzo [b] prepared as described in Example 1, Step 5.
Furan-2-carboxylic acid (1.0 g, 3 mmol) and the product of step 1 above (0.6 g, 3 mmol)
) Was dissolved in dry DCM (100), DMAP (0.4 g, 3 mmol) was added and the mixture was stirred. DCC (0.6 g, 3 mmol) was added and stirring was continued (24 hours). The reaction was monitored by tlc. The precipitate of dicyclohexylurea was filtered and the solvent was removed in vacuo. Flash chromatography of the product [silica gel / petroleum fraction (boiling point 4
0-60 ° C.), DCM 7: 3] and then recrystallisation (hexane). A white solid was obtained. Yield: 0.8 g (52%). Purity (hplc) 99%. ¹ H NMR CD ₂ Cl ₂ / δ 7.91 (1H dd), 7.75 (1H, d), 7.73 (1H, dd), 7.67 (1H, d)
, 7.54 (2K d), 7.28 (2H, d), 7.25 (2H, d), 7.14 (2H, d), 2.65 (2h, t), 2.63 (2H, t), 1.64 (4H, m), 1.31 (16H, m), 0.88 (6H, t) IR (KBr) ν _max / cm ^-1 2920, 1734, 1578, 802 MS m / z 510 (M ⁺ ), 481, 425, 319 (100%), 191

[0161] Example 35 4-butoxy-phenyl 5- (4-heptyl) benzo [b] furan-2-Kishireto compound of Preparation The title (Compound 7 of Table 1), using the following amounts, performed Prepared and purified in a manner similar to that described in Example 34. 5- (4-heptylphenyl) benzo [b] furan-2-carboxylic acid (0.5 g, 1.5 mmol)
4-butoxyphenol (0.3 g, 1.5 mmol), DMAP (0.2 g, 1.5 mmol), D
CC (0.3 g, 1.5 mmol). The product was obtained as a white crystalline solid. Yield: 0.4 g (52%), purity (hplc)> 99%. ¹ H NMR CDCl ₃ / δ 7.89 (1H, dd), 7.75 (1H, s), 7.72 (1H dd), 7.67 (1H, d),
7.54 (2H, d), 7.29 (2H, d), 7.17 (2H, d), 6.95 (2H, d), 3.98 (2H, t), 2.
66 (2H, t), 1.79 (2H, qui), 1.66 (2H, qui) 1.49 (2H, qui), 1.32 (8H, m),
0.99 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2925, 1734, 1502, 1160, 948, 804 MS m / z 484 (M ⁺ ), 319, 264, 166, 69 (100%)

Example 36 Preparation of 4-hexyloxyphenyl 5- (4-heptylphenyl) benzo [b] furan-2- carboxylate (Compound 8 in Table 1) The title compound was prepared in the following amounts: Prepared and purified in a manner similar to that described in Example 34. 5- (4-heptylphenyl) benzo [b] furan-2-carboxylic acid (0.5 g, 1.5 mmol)
4-hexyloxyphenol (0.3g, 1.5mmol), DMAP (0.2g, 1.5mmol)
), DCC (0.3 g, 1.5 mmol). A white crystalline solid was obtained. Yield: 0.3 g (40%), Purity (hplc)> 99.9%. ¹ H NMR CD ₂ Cl ₂ / δ 7.93 (1H, dd), 7.77 (1H, d), 7.75 (1H, dd), 7.68 (1H, d)
7.56 (2H, d), 7.29 (2H, d), 7.16 (2H, d), 6.96 (2H, d) 3.98 (2H, t), 2.
66 (2H t), 1.79 (2H, qui), 1.64 (2H, qui), 1.48 (2H, qui), 1.34 (12H, m)
, 0.93 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2858, 1733, 1502, 1310, 1199, 1160, 1072, 948
, 803 MS m / z 512 (M ⁺ ), 482, 427, 3982 178 (100%)

[0163] Example 37 4-pentylphenyl 5- (4-heptyl) benzo [b] furan-2-Kishireto compound of Preparation The title (Compound 66 of Table 1), using the following amounts, performed Prepared and purified in a manner similar to that described in Example 34. 5- (4-heptylphenyl) benzo [b] furan-2-carboxylic acid (0.5 g, 1.5 mmol)
4-pentylphenol (0.3g, 1.5mmol), DMAP (0.2g, 1.5mmol), D
CC (0.3 g, 1.5 mmol). A white crystalline solid was obtained. Yield: 0.2 g (30%). Purity (hplc)> 97.6%. ¹ H NMR CD ₂ Cl ₂ / δ 7.93 (1H, dd), 7.77 (1H, d), 7.75 (1H, dd), 7.69 (1H, d)
, 7.56 (2H, d), 7.30 (2H, d), 7.27 (2H, d), 7.15 (2H, d), 2.67 (2H, t),
2.64 (2H, t), 1.65 (4H, m), 1.33 (12H, m) 0.91 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2958, 2921, 2852, 1732 , 1303, 1221, 1161, 8037, 741 MS m / z 482 (M ⁺ ), 397, 319 (100%), 263, 178

Example 38 (S)-(+)-4 (2-methylbutyl) phenyl 5- (4-heptylphenyl) benzo [
b] Preparation of furan-2-carboxylate (Compound 11 in Table 1) The title compound was prepared and purified in a similar manner as described in Example 34 using the following amounts. 5- (4-heptylphenyl) benzo [b] furan-2-carboxylic acid (0.5 g, 1.5 mmol)
, (S)-(+)-4 (2-methylbutyl) phenol (0.3 g, 1.5 mmol), DMAP (0.
2 g, 1.5 mmol), DCC (0.3 g, 1.5 mmol). A white crystalline solid was obtained. Yield: 0.5 g (75%). Purity (hplc)> 99.1%. ¹ H NMR CD ₂ Cl ₂ / δ 7.93 (1H, dd), 7.77 (1H, d), 7.75 (1H, dd), 7.69 (1H d)
, 7.56 (2H, d), 7.29 (2H, d), 7.24 (2H, d), 7.16 (2H, d), 2.68 (1H, dd),
2.66 (2H, t), 2.41 (1H dd), 1.66 (3H, m), 1.32 (10H, m), 0.93 (3H, t), 0
.89 (3H, t), 0.87 (3H, d) IR (KBr) ν _max / cm ^-1 2965, 2858, 1735, 1569, 1502, 1294, 1075, 950, 807,
745 MS m / z 482 (M ⁺ ), 397, 319 (100%), 267, 178 [α] _D ^{26 °} ID + 43.3 ° (0.01878 g / ml)

Example 39 (S)-(+)-1-Methylheptyl 5- (4-heptylphenyl) benzo [b] furan-
Preparation of 2-carboxylate (Compound 62 in Table 1) The title compound was prepared and purified in a similar manner as described in Example 34 using the following amounts. 5- (4-heptylphenyl) benzo [b] furan-2-carboxylic acid (0.5 g, 1.5 mmol)
, (S)-(+)-octane-2-ol (0.2g, 1.5mmol), DMAP (0.2g, 1.5mmol)
), DCC (0.3 g, 1.5 mmol). A colorless oil was obtained. Yield: 0.5 g (74%). Purity (hplc) 99.7%. ¹ H NMR CD ₂ Cl ₂ / δ 7.85 (1H, dd), 7.68 (1H, dd), 7.61 (1H, d), 7.53 (1H, d
) 7.52 (2H, d), 7.27 (2H, d), 5.17 (1H, m), 2.64 (2H, t), 1.75 (2H, m), 1.
62 (2H, m), 1.33 (19H, m), 0.88 (3H, t), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2856, 1719, 1539, 1461, 1245, 1165 , 847, 803,
597 MS m / z 448 (M ⁺ ), 363, 336, 251, 57 (100%) [α] _D ^{23 °} ID + 43.3 ° (0.01878 g / ml)

Example 40 Preparation of methyl 5- (4-heptylphenyl) benzo [b] furan-2-carboxylate ( Compound 24 in Table 1) In methanol (5 ml) Compound 43 in Table 1 (0.1 g, 0.3 mmol) ) And sulfuric acid (concentrated) (0.1
The mixture of (ml, 2.0 mmol) was drained of water and refluxed (24 hours). After cooling, the mixture was poured into water (20ml) and DCM was added (20ml). The separated aqueous layer is DCM
Wash with (2 x 20 ml). The combined organic layer was washed with water and brine, dried (MgS
O _4), was eliminated in vacuo the solvent. The product was purified by recrystallization (hexane). A white crystalline solid was obtained. Yield: 0.1 g (95%). Purity (hplc)> 99.5%. ¹ H NMR CD ₂ Cl ₂ / δ 7.88 (1H, d), 7.70 (1H, dd), 7.64 (1H, d), 7.57 (1H, d)
, 7.53 (2H, d), 7.28 (2H, d), 3.95 (3H, s), 2.66 (2H, s), 1.65 (2H, qui)
, 1.32 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 2856, 1736, 1565, 1438, 1164, 1099, 898, 847,
767 MS m / z 350 (M ⁺ ), 293, 265 (100%), 177, 165

Example 41 Preparation of Ethyl 2- (4-heptylphenyl) benzo [b] furan-5-carboxylate ( Compound 64 in Table 1) Compound 64 was prepared for the preparation of compound 24 using the following amounts: Prepared and purified in a similar manner as described. Compound 63 of Table 1 (0.1 g, 0.3 mmol), sulfuric acid (concentrated) (0.1 ml, 0.05 mmol), ethanol (5 ml). Colorless needle-like crystals were obtained. Yield: 0.05 g (46%). Purity (hplc)> 99%. ¹ H NMR CD ₂ Cl ₂ / δ 8.30 (1H d), 7.99 (1H, dd), 7.79 (2H, d), 7.55 (1H, d),
7,30 (2H, d), 7.06 (1H, d), 3.67 (2H, q), 2.66 (2H, t), 1.65 (2H, qui)
, 1.14 (3H, t), 1.30 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2856, 1708, 1616, 1509, 1445, 1172, 1019, 5817 MS m / z 364 (M ⁺ ), 279, 251, 203, 91 (100%),

Example 42 4-Pentylphenyl 2- (4-heptylphenyl) benzo [b] furan-5-carbo
Preparation of Xylates (Compound 65 in Table 1) The title compound was prepared and purified in a similar manner as described for the preparation of compound 34 using the following amounts. Compound 63 of Table 1 (0.3 g, 0.9 mmol), 4-pentylphenol (0.2 g, 0.9 mmol)
), DCC (0.2 g, 0.9 mmol), DMAP (0.1 g, 0.9 mmol). Colorless crystals were obtained. Yield: 0.3 g (67%). Purity (hplc)> 97.1%. ¹ H NMR CD ₂ Cl ₂ / δ 8.46 (1H, d), 8.12 (1H, dd), 7.81 (2H, d), 7.62 1H d),
7.31 2H, d), 7.26 (2H, d), 7.13 (2H, d), 7.11 (1H d), 2.67 (2H, t), 2.65
(2H, t), 1.65 (4H, qui), 1.32 (14H, m), 0.91 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 2857, 1736, 1510 , 1155, 1065, 913, 803, 761 MS m / z 482 (M ⁺ ), 397, 369, 319 (100%), 205

Example 43 4-heptylphenyl 2- (4-heptylphenyl) benzo [b] furan-5-carbo
Preparation of Xylate (Compound 19 in Table 1) The title compound was prepared and purified in a similar manner as described in Example 34 using the following amounts. Compound 63 of Table 1 (0.3 g, 0.9 mmol), 4-heptylphenol (0.2 g, 0.9 mmol)
), DCC (0.2 g, 0.9 mmol), DMAP (0.1 g, 0.9 mmol). White crystals were obtained. Yield: 0.3 g (65%). Purity (hplc)> 99.1%. ¹ H NMR CD ₂ Cl ₂ / δ 8.46 (1H, dd), 8.13 (1H, dd), 7.81 (2H, d), 7.62 (1H, d)
, 7.31 (2H, d), 7.26 (2H, d), 7.13 (2H, d), 7.11 (1H, d), 2.66 (2H, t)
, 2.65 (2H, t), 1.65 (4H, m), 1.32 (16H, m), 0.90 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2857, 1737 , 1510, 1465, 1156, 1065, 914, 838
, 761 MS m / z 510 (M ⁺ ), 425, 318 (100%), 220, 205

Example 44 4-Butoxyphenyl 2- (4-heptylphenyl) benzo [b] furan-5-carbo
Preparation of Xylate (Compound 20 of Table 1) The title compound was prepared and purified in a similar manner as described in Example 34 using the following amounts. Compound 63 of Table 1 (0.3 g, 0.9 mmol), 4-butoxyphenol (0.2 g, 0.9 mmol)
), DCC (0.2 g, 0.9 mmol), DMAP (0.1 g, 0.9 mmol). A white solid was obtained. Yield: 0.3 g (69%). Purity (hplc)> 99%. ¹ H NMR CD ₂ Cl ₂ / δ 8.45 (1H, dd), 8.12 (1H, dd), 7.81 (2H, d), 7.62 (1H, d
), 7.31 (2H, d), 7.13 (2H, d), 7.10 (1H, s), 6.94 (2H, d), 3.99 (2H, d)
, 2.67 (2H, t), 1.78 (2H, qui), 1.65 (2H, qui), 1.51 (2H, m), 1.30 (8H,
m), 0.99 (3H, t), 0.86 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 2858, 1742, 1616, 1510, 1468, 1156, 1068, 913
, 803, 761 MS m / z 484 (M ⁺ ), 399, 319 (100%), 206, 57

Example 45 4-hexyloxyphenyl 2- (4-heptylphenyl) benzo [b] furan-5-
Preparation of Carboxylate (Compound 21 in Table 1) The title compound was prepared and purified in a similar manner as described in Example 34 using the following amounts. Compound 63 of Table 1 (0.3 g, 0.9 mmol), 4-hexyloxyphenol (0.2 g, 0
.9 mmol), DCC (0.2 g, 0.9 mmol), DMAP (0.1 g, 0.9 mmol). A white solid was obtained. Yield: 0.3 g (65%). Purity (hplc)> 99%. ¹ H NMR CD ₂ Cl ₂ / δ 8.43 (1H d), 8.10 (1H, dd), 7.79 (2H, d), 7.60 (1H, d),
7.29 (2H, d), 7.12 (2H, d), 7.08 (1H, s), 6.92 (2H, d), 3.96 (2H, t),
2.65 (2H, t), 1.77 (2H, qui), 1.63 (2H, qui), 1.46 (2H, qui), 1.30 (12H
, m), 0.90 (3H, t), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 2859, 1743, 1615, 1513, 1469, 1159, 1066, 9
16, 835, 803 MS m / z 512 (M ⁺ ), 483, 427, 319 (100%), 291

Example 46 (S)-(+)-4- (2-methylbutyl) phenyl 2- (4-heptylphenyl) benzo [
b] Preparation of Furan-5-carboxylate (Compound 22 in Table 1) The title compound was prepared and purified in a similar manner as described in Example 34 using the following amounts. Compound 63 of Table 1 (0.3 g, 0.9 mmol), 4- (2-methyl-n-butyl) phenol (0
.2 g, 0.9 mmol), DCC (0.2 g, 0.9 mmol), DMAP (0.1 g, 0.9 mmol). White fibrous crystals were obtained. Yield: 0.3 g (69%). Purity (hplc) 98.9%. ¹ H NMR CD ₂ Cl ₂ / δ 8.46 (1H, d), 8.13 (1H, dd), 7.81 (2H, d), 7.62 (1H, d)
, 7.31 (2H, d), 7.23 (2H, d), 7.13 (2H, h), 7.11 (1H, d), 2.69 (3H, m),
2.41 (1H, m), 1.66 (3H, m), 1.32 (10H, m), 0.93 (3H, t), 0.89 (3H, t), 0
.88 (3H, d) IR (KBr) ν _max / cm ^-1 2933, 2858, 1728, 1509, 1124, 1064, 1015, 911, 835
, 798, 760 MS m / z 482 (M ⁺ ), 397, 319 (100%), 206, 57 [α] _D ^{24 °} + 4.0 ° (0.01796 g / ml)

Example 47 Preparation of (S)-(+)-1-methylheptyl 2- (4-heptylphenyl) benzo [b] furan-5 -carboxylate (Compound 23 of Table 1) Prepared and purified in a similar manner as described in Example 34 using the following amounts. Compound 63 of Table 1 (0.3 g, 0.9 mmol), octan-2-ol (0.1 g, 0.9 mmol)
, DCC (0.2 g, 0.9 mmol), DMAP (0.1 g, 0.9 mmol). A white crystalline solid was obtained. Yield: 0.2 g (50%). Purity (hplc) 98.7%. ¹ H NMR CD ₂ Cl ₂ / δ 8.27 (1H, dd), 7.96 (1H, dd), 7.77 (2H, d), 7.52 (1H, d
), 7.28 (2H, d), 7.04 (1H, d), 5.13 (1H, sxt), 2.64 (2H, t), 1.74 (2H, m
), 1.61 (2H, m), 1.30 (19H, m), 0.87 (6H, m) IR (KBr) ν _max / cm ^-1 2933, 2861, 1715, 1595, 1507, 1163, 1087, 797, 765
MS m / z 448 (M ⁺ ), 336, 319, 251, 43 (100%),

Example 48 Preparation of 2,5-bis- (4-heptylphenyl) benzo [b] furan (Compound 66 in Table 1) Step 1: Preparation of 5- (4-heptylphenyl) benzo [b] furan The title compound was prepared in a similar manner as described for the preparation of ethyl 5- (4-heptylphenyl) benzo [b] furan-2-carboxylate in Example 1 (4) using the following amounts: did. Compounds 5-bromobenzofuran (10.0 g, 51 mmol), 4-heptylbenzeneboronic acid (13.4 g, 61 mmol), tetrakis (triethylphosphine) palladium (0) (
0.2 g, 0.2 mmol) sodium carbonate (13.5 g, 128 mmol). The product was purified by flash chromatography [silica gel / petroleum fraction (boiling point 40-60 ° C)] and then recrystallization (petroleum fraction (boiling point 40-60 ° C)). A colorless plate was obtained. Yield: 7.5 g (50%), melting point: 51-3 ° C. ¹ H NMR CDCl ₃ / δ 7,77 (1H, d), 7.64 (1H, d), 7.55 (1H, d), 7.53 (2H, d),
7.51 (1H, dd), 7.26 (2H, d), 6.81 (1H, d), 2.65 (2H, t), 1.65 (2H, q),
1.34 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2921, 1463, 1130, 804, 743 MS m / z 292 (M ⁺ ), 220 207 (100%), 178 , 165,

Step 2 Preparation of 5- (4-heptylphenyl) benzo [b] furan-2-boric acid The title compound was prepared according to the procedure described in Example 20 (2) using the following amounts: Prepared in a manner similar to that described for the preparation of boric acid. 5- (4-heptylphenyl) benzo [b] furan from step 1 (4.0 g, 13.7 mmol),
n-Butyllithium (2.5 M in hexane, 4.5 ml, 11.3 mmol), trimethylborate (2.9 g, 27.4 mmol). A pale pink solid was obtained. Yield: 4.6 g (99%). ¹ H NMR CDCl ₃ / δ 7.82 (1H, d), 7.59 (1H, dd), 7.55 (1H, d), 7.53 (2H, d),
7.41 (1H, d), 7.26 (2H, d), 4.94 (2H, s), 2.65 (2H, t), 1.65 (2H, m), 1
.33 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 3400, 2930, 2850, 1575, 1445, 1330, 1010, 805 MS m / z 336 (M ⁺ ), 292 , 207 (100%), 178, 107

Step 3 Preparation of 2,5-bis- (4-heptylphenyl) benzo [b] furan (Compound 66) Compound 66 was prepared as described in Example 1 (4) using the following amounts. Prepared in a similar manner. 5- (4-heptylphenyl) benzo [b] furan-2-boric acid (1.5 g, 4.5 mmol), 1-
Bromo-4-heptylbenzene (0.8 g, 3.7 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol), sodium carbonate (1.0 g, 9.3 mmo
l). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C), DCM 9: 1] and then recrystallization (acetonitrile, toluene 5: 1). A colorless crystalline solid was obtained. Yield: 0.4 g (26%). Purity (hplc) 98.6%. ¹ H NMR CD ₂ Cl ₂ / δ 7.78 (2H, d), 7.75 (1H, dd), 7.54 (2H, d), 7.53 (1H, d)
, 7.48 (1H, dd), 7.28 (2H, d), 7.24 (2H, d), 7.03 (1H, d) 2.53 (4H, t), 1
.52 (4H, m), 1.06 (16H, m), 0.57 (6H, t) IR (KBr) ν _max / cm ^-1 2920, 1465, 1160, 1015, 845, 800 MS m / z 466 (M ⁺ ), (100%), 381, 309, 296, 252

Example 49 Preparation of 5- (4-heptylphenyl) -2- (4-pentylphenyl) -benzo [b] furan ( Compound 67 of Table 1) The title compound was prepared in the following amounts: Prepared and purified in a manner similar to that described for the preparation of compound 66 in Example 48. 5- (4-heptylphenyl) benzo [b] furan-2-boric acid (1.5 g, 4.5 mmol), 1-
Bromo-4-pentylbenzene (0.8 g, 3.7 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol), sodium carbonate (1.0 g, 9.3 mmo
l). A white crystalline solid was obtained. Yield: 0.4 g (20%). Purity (hplc) 98.5%. ¹ H NMR CD ₂ Cl ₂ / δ 7.80 (2H, d), 7.77 (1H, dd), 7.54 (2H, d), 7.54 (1H, d),
7.50 (1H, dd), 7.29 (2H, d), 7.27 (2H, d), 7.05 (1H, d), 2.67 (2H, t),
2.66 (2H, t), 1.66 (4H, m), 1.33 (12H, m), 0.91 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2961, 2857, 1465, 908, 801 MS m / z 438 (M ⁺ ), 381, 353, 296 (100%), 283

Example 50 Preparation of 2- (5-heptylpyrimidin-2-yl) -5- (4-heptylphenyl) -benzo [b] furan (Compound 68 in Table 1) The title compound was prepared in the following amounts: Was prepared and purified in the same manner as described in Example 1 (4). 5- (4-heptylphenyl) benzo [b] furan-2-boric acid (1.5 g, 4.5 mmol), 2-
Chloro-5-heptylpyrimidine (0.8 g, 3.7 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol), sodium carbonate (1.0 g, 9.3 mmol)
). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C), DCM 1: 1] and then recrystallisation (hexane). Colorless needle-like crystals were obtained. Yield: 0.8 g (46%). Purity (hplc)> 99.9%. _{^{1 H NMR CDCl 3/6 8.67}} (2H, s), 7.85 (1H, d), 7.69 (1H, d), 7.69 (1H, d),
7.60 (1H, dd), 7.55 (2H, d), 7.28 (2H, d), 2.68 (4H, t), 1.67 (4H, m), 1
.34 (16H, m), 0.89 (6H, t) IR (KBr) ν _max / cm ^-1 2923, 2852, 1577, 1542, 1425, 1153, 804, 795 MS m / z (468 ⁺ ), 383 ( 100%), 311, 298, 232

Example 51 2- (3,4 difluorophenyl) -5- (4-heptylphenyl) benzo [b] furan
Preparation of (Compound 69 in Table 1) The title compound was prepared and purified in a similar manner as described in Example 1 (4) using the following amounts. 5- (4-heptylphenyl) benzo [b] furan-2-boric acid (0.4 g, 1.2 mmol), 1-
Bromo-3,4-difluorobenzene (0.2 g, 1.1 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol), sodium carbonate (1.0 g, 9.3 mmol)
). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C)], and then recrystallization (ethanol). Colorless crystals were obtained. Yield: 0.1 g (12%). Purity (hplc) 98%. ¹ H NMR CD ₂ Cl ₂ / δ 7.79 (1H dd), 7.72 (1H7 ddd), 7.65 (1H, m), 7.58 (2K d)
, 7.57 (1H, d), 7.54 (1H, dd), 7.29 (1H, m), 7.28 (1H, m), 7.08 (1H, s)
, 2.66 (2H, qui), 1.65 (2H. Qui), 1.32 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2925, 2857, 1515, 1468, 1180, 874, 798, 772 MS m / z 707 (M ⁺ ), 319 (100%), 305, 289, 159

[0180]   Example 52   2- (2,3-difluoro-4-heptylphenyl) -5- (4-heptylphenyl) ben Preparation of Zo [b] furan (Compound 70 in Table 1)   Process 1   Preparation of 1- (2,3-difluorophenyl) heptan-1-ol   n-Butyllithium (2.5M in hexane, 140.0 ml, 350.0 mmol) was stirred under nitrogen.
To a cooled (-78 ° C) solution of O-difluorobenzene in dry THF (400 ml),
Added drop by drop. Continue stirring at low temperature (1 hour and a half), n-heptanal (40.1
g, 333.0 mmol) was added dropwise. Allow the mixture to warm to room temperature and stir overnight under nitrogen.
It was 2M hydrochloric acid (225 ml) was added and stirring was continued (1 hour). Mix the mixture in water (400
ml) and ether was added (200 ml). The separated aqueous layer was washed with ether (2 x 3
It was washed with 00 ml). The mixed ether layer was washed with water and brine, dried (MgSO4). _Four ), The solvent was removed in vacuo. The residue was distilled. A pale yellow oil was obtained.   Yield: 63.1g (83%), Boiling point: 0.001mmHg 140 ℃¹ H NMR CD₂Cl₂/ δ 7.24 (1H, m), 7.10 (2H, m), 5.00 (1H, t), 2.25 (1H, s),
 1.75 (2H, m), 1.30 (8H, m), 0.88 (3H, t) IR (KBr) ν_max/cm^-1  3369, 2931, 1626, 1596, 1484, 1278, 1203, 1061, 786
, 726 MS m / z 228 (M⁺), 211, 199, 143 (100%), 127

Step 2 Preparation of 1- (2,3-difluorophenyl) hept-1-ene 1- (2,3-difluorophenyl) heptan-1-ol of step 1 (61.1 g, 267.0 m
mol) in heptane (90 ml) was carefully added phosphorus pentoxide (94.9 g, 669.0 mmol) to exclude water and the mixture was stirred overnight. When glc analysis showed the reaction was complete, the mixture was poured into ice / water (300 ml) and ether was added (200 ml). The separated aqueous layer was washed with ether (2 x 300 ml). The combined organic layers were washed with water and brine, dried (MgSO _4), and removed the solvent in vacuo. The residue was distilled. A colorless oil was obtained. Yield: 30.9g (55%), Boiling point: 95mmC at 0.05mmHg. ¹ H NMR CDCl ₃ / δ 7.16 (1H, m), 6.97 (2H, m), 6.51 (1H, d), 6.34 (1H, dt)
2.23 (2H, q), 1.48 (2H, qui), 1.34 (4H, m), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 1621, 1589, 1482, 1205, 972, 773 , 712 MS m / z 210 (M ⁺ ), 167, 153, 140 (100%), 127

Step 3 Preparation of 1,2-difluoro- 3 - heptylbenzene In ethanol (400 ml) the product of step 2 (30.5 g, 145 mmol) and palladium on charcoal (10% w / w, 1.0 g, 0.9 mmol). ) Was stirred under an atmosphere of hydrogen (glc analysis showed the reaction was complete). The mixture was filtered through a pad of'Hyflo Supercel 'and the solvent removed in vacuo. The product was purified by distillation. A pale yellow liquid was obtained. Yield: 26.4g (86%), Boiling point: 0.003mmHg, 95 ° C. ¹ H NMR CDCl ₃ / δ 6.95 (3H, m), 2.65 (2H, t), 1.60 (2H, qui), 1.31 (8H, m)
, 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2929, 2858, 1628, 1595, 1490, 1209, 822, 780, 725 MS m / z 212 (M ⁺ ), 141, 127 (100% ), 114, 83

Step 4 Preparation of 2,3-difluoro-1-iodo- 4 - heptylbenzene In dry THF (100 ml) a cold (-78 ° C) solution of the product of step 3 (7.0 g, 33.0 mmol) was added nitrogen. While stirring under stirring, n-butyllithium (2.5M in hexane, 14.4 ml, 36.0
mmol) was added drop by drop. Stirring at low temperature was continued (1 h) and iodine (8.4 g, 33.0 mmol) in dry THF (100 ml) was added drop wise, keeping the temperature low. The mixture was warmed to room temperature and stirred overnight under nitrogen. It was poured into water (50 ml) and ether was added (50 ml). The separated aqueous layer was washed with ether (2 × 50 ml), the mixed organic layer was washed with a saturated aqueous solution of sodium sulfite, water and brine, and dried (MgS
O _4), was eliminated in vacuo the solvent. The product was purified by distillation. A pale pink liquid was obtained. Yield: 5.0 g (45%), Boiling point: 0.005 mmHg, 125 ° C. ¹ H NMR CDCl ₃ / δ 7.37 (1H ddd), 6.73 (1H, ddd), 2.63 (2H, dt), 1.58 (2H,
t), 1.29 (8H, in), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2927, 2856, 1457, 1285, 866, 806, 724, 612, 546 MS m / z 338 (M ⁺ ), 254, 139, 127 (100%), 107

[0184] Step 5 2- (2,3-Difluoro-4-heptyl-phenyl) -5- (4-heptyl-phenyl) Ben zo [b] furan compounds 70 Preparation Table 1 is carried out using the following amounts Prepared in a manner similar to that described for the preparation of compound 66 in Example 48 (3). 5- (4-heptylphenyl) benzo [b]
Furan-2-boric acid (0.6 g, 1.8 mmol), the product of Step 4 (0.6 g, 1.6 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.31 mol), sodium carbonate (0.4 g, 4.0 mmol). The product was purified by flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C.)] and then recrystallisation (hexane). A white crystalline solid was obtained. Yield: 0.3 g (37%). Purity (hplc)> 99%. ¹ H NMR CD ₂ Cl ₂ / δ 7.81 (1H dd), 7.69 (1H, ddd), 7.57 (2H, 7.56 (214, d),
7.28 (2K d), 7.25 (1H, dd), 7.10 (1H, ddd), 2.72 (2H, t), 2.66 (2H, t),
1.65 (4H, qui), 1.33 (16H, m), 0.89 (61L t) IR (KBr) ν _max / cm ^-1 2927, 2856, 1498, 1123, 965, 878, 809, 726 MS m / z 502 ( M ⁺ ) (100%), 417, 332, 166, 58

Example 53 Preparation Step for 2- (Hept-1-ynyl) -5- (4-heptylphenyl) benzo [b] furan ( Compound 17 in Table 1 ) 1 2-Iodo-5- (4-heptyl Preparation of ( phenyl) benzo [b] furan 5- (4-heptylphenyl ) benzo [b] n-butyllithium (2.5M in hexane, 3.8ml, 9.4mmol) in dry THF (400ml) stirred under nitrogen. ] Fran (2.5g, 8.
6 mmol) (prepared as described in Example 48 (1)) to a cooled (-78 ° C) solution was added dropwise. Stirring at low temperature was continued (2 hours) and iodine (4.3 g, 17.2 mmol) in dry ether (30 ml) was added dropwise. After stirring for an additional 30 minutes at low temperature, the mixture was allowed to come to room temperature. It was poured into water (50 ml) and ether was added (50 ml). The separated aqueous layer was washed with ether (2 x 50 ml). Saturated aqueous sodium sulfite solution mixed ether layer was washed with water and brine, dried (MgSO _4). The solvent was removed in vacuum. The product was purified by recrystallization (hexane). Colorless plate-like crystals were obtained. Yield: 2.5 g (70%), melting point: 94-95 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.71 (1H, d), 7.52 (1H, d), 7.51 (2H, d), 7.46 (1H, dd)
, 7.04 (1H, d), 2.65 (2H, t), 1.64 (2H, qui), 1.31 (8H, m), 0.89 (3H, t)
IR (KBr) ν _max / cm ^-1 2922, 2849, 1524, 1446, 1232, 1147, 1048, 918, 897,
884, 668 MS m / z 418 (M ⁺ ), 333, 207, 178, 43 (100%),

[0186]   Process 2   Preparation of 2- (hepto-1-ynyl) -5- (4-heptylphenyl) benzo [b] furan   n-Butyllithium (2.5M in hexane, 2.8ml, 6.9mmol) is being stirred under nitrogen
A solution of hept-1-yne (0.6 g, 6.3 mmol) in cold (-40 ml) in dry THF.
Was added drop by drop. Continue stirring at low temperature (20 minutes) and dry while maintaining low temperature.
A solution of anhydrous zinc chloride (1.1 g, 8.0 mmol) in dry THF (30 ml) was added dropwise.
. Stirring under nitrogen was continued (4 hours) and the mixture was allowed to come to room temperature. Product of Step 1 (2.4
g, 5.7 mmol) and tetrakis (triethylphosphine) palladium (0) (0.2
g, 0.2 mmol) was added, and the mixture was heated (70 ° C.) with stirring under nitrogen (12:00).
while). When glc / tlc analysis showed no further reaction, the mixture was washed with water.
Pour into medium (50 ml) and add ether (50 ml). The separated aqueous layer was washed with ether (
2 × 50 ml). The combined organic layers were washed with water and brine, dried (MgSO4). _Four ), The solvent was removed in vacuo. Flash chromatography of the product
Oil / petroleum fraction (boiling point 40-60 ° C.)]. A yellow crystalline solid is obtained
It was   Yield: 0.9 g (42%). Purity (hplc) 99.5%.¹ H NMR CD₂Cl₂/ δ 7.72 (1H d), 7.54 (1H, dd), 7.53 (2H, d), 7.47 (1H, d),
  7.27 (2H, d), 6.88 (1H, s), 2.65 (2H, t), 2.51 (2H, t), 1.67 (4H, m),
1.40 (12H, m), 0.95 (3H, t), 0.90 (3H, t) IR (KBr) ν_max/cm^-1 2929, 2859, 2210, 1570, 1265, 992, 886, 842, 749, 727
MS m / z 386 (M⁺), 371, 301 (100%), 244, 207

[0187] Example 54 2- (4-heptyl-phenyl) -5- (hept-1 Inirufeniru) benzo [b] furan Preparation of (Table 1 Compound 71) Step 1 5- (hept-1 Inirufeniru) benzo [b] Preparation of Furan The title compound was prepared and purified in a similar manner as described for the preparation of compound 17 in Example 53, using the following amounts. n-Butyllithium (2.5 in hexane
M, 4.8 ml, 12.0 mmol), hept-1-yne (1.1 g, 11.0 mmol), zinc chloride (1.9 g, 1
4.0 mmol), 4-bromobenzofuran (2.0 g, 10.0 mmol). A yellow liquid was obtained. Yield: 1.2 g (57%). ¹ H NMR CD ₂ Cl ₂ / δ 7.65 (2H, d), 7.42 (1H, d), 7.33 (1H, dd), 6.76 (1H, dd
), 2.42 (2H, t), 1.63 (2H, qui), 1.41 (4H, m), 0.94 (3H, t) IR (KBr) ν _max / cm ^-1 2936, 2866, 1465, 1131, 1032, 883 , 768, 735 MS m / z 212 (M ⁺ ), 197, 183, 169, 154 (100%)

Step 2 Preparation of 5- (hept-1-ynylphenyl) benzo [b] furan-2-boric acid The title compound was prepared as described in Example 20 (2) using the following amounts: Was prepared and purified by the method 5- (Hept-1-ynylphenyl) benzo [b] furan from Step 1 (1.0 g, 5.2 mmol
), N-butyllithium (2.5 M in hexane, 2.3 ml, 5.7 mmol), trimethylborate (1.2 g, 11.4 mmol). An orange solid was obtained. Yield: 1.0 g (83%). MS m / z 232 (M ⁺ ), 212, 183, 169, 155 (100%)

Step 3 Preparation of 2- (4-heptylphenyl) -5- (hept-1-ynylphenyl) benzo [b] furan (Compound 71 of Table 1) The title compound was prepared using the following amounts: Prepared and purified in a similar manner as described for the preparation of compound 70 in Example 52. 5- (Hept-1-ynylphenyl) benzo [b] furan-2-borate from Step 2 (1.0 g, 4.3 mmol), 1-Bromo-4-heptylbenzene (Example 1 (1)) (1.1 g , 4.3mmol), tetrakis (triethylphosphine) palladium (0) (0.2g, 0.2mmol), sodium carbonate (1.1g, 11.0)
mmol). Yield: 0.3 g (18%). Purity (hplc) 85.1%. ¹ H NMR CD ₂ Cl ₂ / δ 7.76 (2H, d), 7.61 (1H, d), 7.42 (1H, d), 7.29 (1H, dd)
, 7.28 (2H, d), 6.96 (1H, s), 2.65 (2H, t), 2.42 (2H, t), 1.63 (4H, qui)
, 1.35 (12H, m), 0.94 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2935, 2859, 1906, 1700, 1653, 1636, 1467, 1274, 878,
798 MS m / z 386 (M ⁺ ) (100%), 343, 301, 244, 215

Example 55 2- (4-heptylphenyl) -5- (4-pentylphenyl) benzo [b] furan (Table
Preparation Step 1 of Compound 72) 1 Preparation of 1 -heptyl-4-iodobenzene The title compound was prepared and purified in a similar manner as described in Example 1 (1) using the following amounts. . Iodobenzene (20.4g, 100mmol), n-heptanoyl chloride (17.8g, 120mmol)
, Ammonium chloride (14.7 g, 110 mmol), poly (methylhydrosiloxane) (16.1 g
g, 267 mmol). Compounds were prepared and stored with exclusion of light. A pale yellow liquid was obtained. Yield: 12.2g (40%), boiling point: 120 ℃ (. Lit 165 ℃ at ² 10 mmHg) at 0.005MmHg.
¹ H NMR CD ₂ Cl ₂ / δ 7.60 (2H, d), 6.96 (2H, d), 2.51 (2H, t), 1.60 (2H, m),
1.35-1.25 (8H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2926, 2854, 1466, 1062, 995, 794 MS m / z 3 02 (M ⁺ ) (100%) , 259, 231, 217, 127

Step 2 Preparation of 2- (4-heptylphenyl) -5-bromobenzo [b] furan The title compound was prepared in a similar manner as described in Example 1 (4) using the following amounts: Prepared and purified. 1-heptyl-4-iodobenzene from step 1 (2.1 g, 7.0 mmol), 4-bromobenzo [b] furan-2-boric acid (2.0 g, 8.0 mmol), sodium carbonate (1.9 g, 18.0 mmo)
l), tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol
). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C)] and then recrystallization (hexane). A white solid was obtained. Yield: 0.5 g (20%), melting point: 144-149 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.68 (2H, d), 7.62 (1H, d), 7.32 (1H, d), 7.28 (1H, dd
), 7.20 (2H, d), 6.87 (1H, s), 2.57 (2H, t), 1.56 (2H, t), 1.23 (8H, m),
0.80 (3H, t) IR (KBr) ν _max / cm ^-1 2930, 2858, 1609, 1582, 1035, 922, 895, 670, 505 MS m / z 372,370 (M ⁺ ), 285 (100%), 205 , 176, 152

Step 3 Preparation of 2- (4-heptylphenyl) -5- (pentylphenyl) benzo [b] furan ( Compound 72 in Table 1 ) The title compound was prepared according to the procedure described in Example 1 ( Prepared and purified by a method similar to that described in 4). 2- (4-heptylphenyl) -5-bromobenzo [b] furan (0.4 g, 1.1 mmol), 4-
Pentylbenzene boric acid (0.3g, 1.3mmol), sodium carbonate (0.3g, 2.8mmol)
, Tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol).
The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C)] and then recrystallization (hexane). A white crystalline solid was obtained. Yield: 0.4 g (83%). Purity (hplc) 98.4%. ¹ H NMR CD ₂ Cl ₂ / δ 7.79 (2H, d), 7.77 (1H, d) 7.56 (1H, d), 7.55 (2H, d),
7.50 (1H, dd), 7.30 (2H, d), 7.28 (2H, d), 7.05 (1H s), 2.66 (4H, t) 1.6
6 (4H, m), 1.33 (12H, m), 0.92 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2963, 2928, 2858, 1589, 1121, 1034, 884 , 799 MS m / z 438 (M ⁺ ), 381, 353, 296, 43 (100%)

Example 56 Preparation Step 1 of Compound 73 in Table 1 Preparation of 1 -heptyl-2,3-difluorobenzene-4-boric acid The title compound was prepared according to the procedure described in Example 20 (2) using the following amounts. Prepared in a manner similar to that described for the preparation of 4'-pentylbiphenyl boric acid in: 1,2-difluoro-3-heptylbenzene (19.2g, 90.0, prepared as described in Example 52 (3). mmol), n-butyllithium (2.5 M in hexane, 39.8 ml, 99.0 mmol
), Trimethylborate (18.7 g, 180.0 mmol). A white solid was obtained. Yield: 19.9 g (87%). ¹ H NMR DMSO-d ⁶ / δ 7.11 (1H, m), 7.10 (1H, m), 2.62 (2H, dt), 1.54 (2H, q
ui), 1.24 (8H, m), 0.84 (3H, t) (acidic proton was not shown) IR (KBr) ν _max / cm ^-1 3661, 3342, 2939, 2849, 1628, 1425, 1190, 929, 902 ,
835, 723 MS m / z 212 (M ⁺ -B (OH) ₂ + H), 169, 140, 128 (100%), 101

Step 2 Preparation of 5- (2,3-difluoro-4-heptylphenyl) benzo [b] furan The title compound was prepared as described in Example 1 (4) using the following amounts: It was prepared by the method. 4-Bromobenzofuran (1.8 g, 9.0 mmol), 1-heptyl-2,3-difluorobenzene-4-boric acid from step 1 (2.8 g, 10.8 mmol), sodium carbonate (2.4 g, 23.0)
mmol), tetrakis (triethylphosphine) palladium (0) (0.3g, 0.3mm
ol). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C)] and then recrystallization (hexane). A pale yellow liquid was obtained. Yield: 1.4 g (47%). ¹ H NMR CD ₂ Cl ₂ / δ 7.77 (1H, s), 7.70 (1H, d), 7.58 (1H, dd), 7.46 (1H, dd
d), 7.16 (1H ddd), 7.04 (1H, ddd), 6.85 (1H, d), 2.71 (2H, t), 1.66 (2H,
qui), 1.38 (8H, m), 0.91 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2861, 1468,1113, 890, 808, 772, 739 MS m / z 328 (M ⁺ ) , 243, 231, 194, 43 (100%)

Step 3 Preparation of 5- (2,3-difluoro-4-heptylphenyl) benzo [b] furan-2-boric acid
Preparation The title compound was prepared in a similar manner as described for the preparation of 4'-pentylbiphenylboric acid in Example 20 (2) using the following amounts. Step 2 product (1.2 g, 3.7 mmol), n-butyllithium (2.5 M in hexane, 1.6 m
l, 4.0 mmol), trimethylborate (0.8 g, 7.4 mmol). A white solid was obtained. Yield: 1.1 g (80%). MS m / z 328 (M ⁺ -B (OH) ₂ ), 256,243 (100%), 201, 175

Step 4 5- (2,3-Difluoro-4-heptylphenyl) -2- (4-heptylphenyl) -be
Preparation of Nzo [b] furan (Compound 73 in Table 1) The title compound was prepared in a similar manner as described in Example 1 (4) using the following amounts. 1-Bromo-4-heptylbenzene (0.8 g, 3.0 mmol), 5- (2,3-difluoro-4-heptylphenyl) benzo [b] furan-2-borate from step 3 (1.1 g, 3.0 mmol) )
, Sodium carbonate (0.8 g, 8.0 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol). A white fibrous crystalline solid was obtained. Yield: 0.4 g (27%). Purity (hplc) 98.4%. ¹ H NMR CD ₂ Cl ₂ / δ 7.80 (2H, d), 7.73 (1H, m), 7.58 (1H, d), 7.43 (1H, ddd
), 7.30 (2H, d), 7.18 (1H, m), 7.05 (1H, d), 7.04 (1H, m), 2.71 (2H, t),
2.66 (2H, t), 1.66 (4H, m), 1.33 (16H, m), 0.90 (3H, t), 0.89 (3H, t)
IR (KBr) ν _max / cm ^-1 2936, 2856, 1509, 1121, 1033, 916, 802, 754 MS m / z 502 (M ⁺ ), 417, 332, 224, 91 (100%)

Example 57 Preparation Step 1 of Compound 74 in Table 1 Preparation of 5- (5-heptylpyrimidin-2-yl) benzo [b] furan The title compound was prepared by using the following amounts: Prepared and purified in a similar manner as described for the preparation of 68. Benzo [b] furan-5-boric acid (Example 22 (1)) (0.7 g, 4.2 mmol), 2-chloro
-5-heptylpyrimidine (0.8g, 3.7mmol), tetrakis (triethylphosphine) palladium (0) (0.1g, 0.1mmol), sodium carbonate (0.9g, 8.8mmol)
. A pale yellow waxy solid was obtained. Yield: 0.9 g (83%). ¹ H NMR CDCl ₃ / δ 8.69 (1H, d), 8.62 (2H, s), 8.42 (1H, dd), 7.65 (1H, d
), 7.58 (1H, d), 6.84 (1H, dd), 2.61 (2H, t), 1.65 (2H, qui), 1.31 (8H,
m), 0.87 (3H, t) IR (KBr) ν _max / cm ^-1 2928, 2856, 1588, 1547, 1130, 1029, 796, 768, 737 MS m / z 294 (M ⁺ ), 265, 251, 223, 209 (100%)

Step 2 Preparation of 5- (5-heptylpyrimidin-2-yl) benzo [b] furan-2-boric acid n-Butyllithium (2.5 M in hexane, 2.0 ml, 5.1 mmol) was stirred under nitrogen. Cooling of dry diisopropylamine (2.0 g, 20.0 mmol) in dry THF (15 ml)
-70 ° C) was added drop-wise to the solution. Stirring was continued (10 min) and at −70 ° C. in dry THF (7 ml) 5- (5-heptylpyrimidin-2-yl) benzo [b] furan from step 1 was added dropwise. After stirring under nitrogen (30 minutes), at low temperature, trimethylborate (1.0
g, 10.0 mmol) was added dropwise. The system was allowed to come to room temperature overnight with stirring under nitrogen. Hydrochloric acid (5M, 4.0 ml) was added with stirring. Pour the mixture into water (100m
l), ether was added (50 ml). The separated aqueous layer was washed with ether (3 x 50 ml). The combined organic layers were washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The residue was adsorbed onto silica and washed with petroleum fraction (bp 40-60 ° C). The adsorbate was washed with THF and the solvent removed in vacuo. An orange solid was obtained. Yield: 1.4 g (78%). MS m / z 294 (M ⁺ -B (OH ₂ ), 223, 209 (100%), 195, 181

[0199] Step 3 2- (2,3-Difluoro-4-heptyl) -5- (5-heptyl-2-yl) Baie emission zone [b] furan compound of Preparation The title (Compound 74), following Was prepared in a similar manner as described for the preparation of compound 68 in Table 1. 5- (5-heptylpyrimidin-2-yl) benzo [b] furan-2-borate (1.3 g, 3.8 mmol) from step 2 2,3-difluoro-1-iodo-4-heptylbenzene (implemented Example 52 (4)) (1.5 g, 4.6 mmol), tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol), sodium carbonate (1.2 g, 12.0 mmol). The product is
Flash chromatography [silica gel / petroleum fraction (boiling point 40-60 ℃), DCM
7: 3], followed by recrystallization (ethanol, DCM 9: 1) and finally by preparative hplc (acetonitrile, chloroform 4: 1). Colorless needle-like crystals were obtained. Yield: 0.4 g (17%). Purity (hplc)> 99.9%. ¹ H NMR CD ₂ Cl ₂ / δ 8.71 (1H, d), 8.62 (2H, s), 8.44 (1H, dd), 7.68 (1H, dd
d), 7.59 (1H, d), 7.27 (1H, dd), 7.09 (1H, ddd), 2.70 (2H, t), 2.62 (2H,
t), 1. 66 (2H, qui), 1. 64 (2H, t), 1.36-1.24 (16H, m), 0.87 (6H, t) IR (KBr) ν _max / cm ^-1 2932, 2859, 1586, 1549, 1328, 1117, 964, 875, 797 MS m / z 504 (M ⁺ ) (100%), 462, 433, 419, 321

Example 58 Preparation Step 1 of Compound 75 in Table 1 Preparation of 1,2-difluorobenzene-3-boric acid The title compound was prepared as described in Example 20 (2) using the following amounts. Prepared in a similar manner to. O-difluorobenzene (65.8g, 577.0mmol), n-butyllithium (in hexane)
2.5M, 231.0 ml, 577 mmol), trimethylborate (71.9 g, 692.0 mmol). The reaction mixture was poured into water (200 ml) and ether was added (200 ml). The separated aqueous phase was washed with ether (3 x 200 ml). The product was extracted from the mixed ether phase as potassium salt by washing with potassium hydroxide (2M, 290 ml).
The base solution was washed with ether and hydrochloric acid (conc.) Was added to the aqueous solution to acidify to pH 3 to release the product. The product was extracted with ether (3 x 200 ml). The combined organic layers were washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. A white solid was obtained. Yield: 47.1 g (52%). MS m / z 420 (3M ⁺ -3H ₂ O) (100%), 280, 140, 94, 75

Step 2 Preparation of 2,3-difluorophenol Hydrogen peroxide (100vol, 197.0ml, 1.74mmol) was added in dry diethyl ether (300ml).
) 1,2-Difluorobenzene-3-boric acid (458.g, 290.0 mmol) was slowly added to a stirred solution and the mixture was refluxed (2 hours). After cooling, the mixture was washed with ether (3x
It was washed with 250 ml). Saturated aqueous solution of sodium thiosulfate mixed ether layer was washed with water and brine, dried (MgSO _4), and eliminated in vacuo the solvent. The product was purified by distillation. A colorless liquid was obtained, which solidified on cooling. Yield: 24.2 g (64%), Boiling point: 760 mmHg, 150 ° C. ¹ H NMR CDCl ₃ / δ 6.95 (1H, m), 6.75 (2H, m), 4.95 (1H, s) IR (KBr) ν _max / cm ^-1 3187, 2986, 1623, 1534, 1196, 1023, 889 , 773, 701 MS m / z 130 (M ⁺ ) (100%), 101, 82, 71, 56

Step 3 Preparation of 4-Bromo-2,3-difluorophenol While maintaining glacial acetic acid (45 ml) bromine (29.1 g, 182.0 mmol) at low temperature, glacial acetic acid /
2,3-Difluorophenol (21.4g, 165.0mmol) in chloroform 4: 1 (55ml)
Was added dropwise to the vigorously stirred, cooled (10 ° C.) solution. Continue stirring (15 minutes),
The mixture was poured into water (200ml) and DCM was added (100ml). The separated aqueous layer was washed with DCM (3 × 100 ml) and the combined organic layer was saturated aqueous sodium hydrogen carbonate solution,
Washed with water and brine, dried (MgSO _4). The solvent was removed in vacuum. Hexane (100 ml) was added to the residue and the mixture was heated until homogeneous. It was cooled (8 ° C.) and the solvent was removed by filtration. The product was distilled. A colorless liquid was obtained. Yield: 26.7 (77%), Boiling point: 135-160 ° C at 20 mmHg. ¹ H NMR CDCl ₃ / δ 7,22 (1H, m), 6.71 (1H, m), 5.57 (1H, s) IR (KBr) ν _max / cm ^-1 3395, 2970, 1622, 1187, 1032, 876 , 798, 630, 535 MS m / z 210, 208 (M ⁺ ), 179, 128, 101, 81 (100%) NMR showed a purity of about 33% consisting of starting material and dibrominated product. Further purification was performed after the next synthetic step.

Step 4 2- (4-Bromo-2,3-difluorophenoxy) acetaldehyde dimethylacetate
Preparation of tar The title compound was prepared in a similar manner as described in Example 9 (1) using the following amounts. The product of Step 3 (28.6 g, 137.0 mmol), bromoacetaldehyde dimethyl acetal (25.5 g, 151.0 mmol), potassium carbonate (37.9 g, 274.0 mmol) and potassium iodide (1.1 g, 7.0 mmol). Flash chromatography of the crude product [neutral alumina / petroleum fraction (boiling point 40-6
0 ° C.), DCM 10: 3] and then by distillation. A colorless liquid was obtained. Yield: 17.4g (46%), Boiling point: 127mm at 0.05mmHg. ¹ H NMR CDCl ₃ / δ 7.21 (1H m), 6.70 (1H, m), 4.71 (1H, t), 4.05 (2H, d),
3.47 (6H, s) IR (KBr) ν _max / cm ^-1 2945, 2842, 1619, 1504, 1140, 880, 795, 593 MS m / z 298,296 (M ⁺ ), 265, 235, 207, 75 (100 %)

Step 5 Preparation of 5 -Bromo-6,7-difluorobenzo [b] furan The title compound was prepared according to the procedure described in Example 9 (2) using the following amounts. Prepared and purified in a similar manner as described. The product of step 4 (9.7 g, 33.0 mmol), polyphosphoric acid (13.9). The product was further purified by recrystallization (ethanol). White needle-like crystals were obtained. Yield: 1.9 g (25%), melting point: 96.5-98.0 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.73 (1H, d), 7.58 (1H, dd), 6.80 (1H, dd) IR (KBr) ν _max / cm ^-1 1603, 1485, 1125, 1084, 876, 814 , 765, 730, 640, 531
MS m / z 234,232 (M ⁺ ), 153, 125, 105 (100%), 77

Step 6 Preparation of 5-Bromo-6,7-difluorobenzo [b] furan-2-boric acid The title compound was prepared from 5- (5-heptylpyrimidin-2-yl) using the following amounts: Prepared and purified in a similar manner as described for the preparation of benzo [b] furan-2-boric acid (Example 57 (2)). n-Butyllithium (2.5 M in hexane, 5.2 ml, 13.0 mmol), dry diisopropylamine (1.3 g, 13.0 mmol), product of step 5 (3.0 g, 13.0 mmol), trimethylborate (2.7 g, 26.0 mmol) , Hydrochloric acid (5M, 5.2 ml). A cream colored solid was obtained. Yield: 3.1 g (86%). MS m / z 777,775 (3M ⁺ -3H ₂ O 705 (100%), 626, 231, 124

Step 7 Preparation of 5-bromo-6,7-difluoro-2- (4-pentylphenyl) benzo [b] furan
Preparation The title compound was prepared and purified in a similar manner as described for the preparation of 5- (4-pentylphenyl) benzo [b] furan (Example 24 (1)) using the following amounts. 4-Iodo-4-pentylbenzene (Example 22 (2)) (1.8 g, 6.7 mmol), Step 6
(1.6 g, 5.6 mmol), sodium carbonate (1.8 g, 17.0 mmol), tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol). A white crystalline solid was obtained. Yield: 1.2 g (57%), melting point: 62-64 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.76 (2H, d), 7.54 (1H, dd), 7.30 (2H, d), 6.96 (1H, d)
, 2.66 (2H, t), 1.65 (2H, qui), 1.34 (4H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2932, 2866, 1605, 1442, 1043, 909, 795, 548 MS m / z 380,378 (M ⁺ ), 321 (100%), 241, 213, 193

[0207] Step 8 6,7-difluoro-5- (4-heptyl) -2- (4-pentylphenyl) Ben zo [b] furan compound of Preparation The title (Compound 75 of Table 1), the following Prepared in a similar manner as described in Example 1 (4) using the amounts. Product of Step 7 (1.2 g, 3.2 mmol), 4-heptylbenzeneboric acid (0.9 g, 3.8 mmo)
l), sodium carbonate (0.9 g, 8.0 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C)] and then recrystallization (ethanol). It was dissolved in carbon tetrachloride / chloroform 19: 1. The solution was triturated with methanol and the precipitate was filtered and washed with ethanol. Colorless needle-like crystals were obtained. Yield: 0.4 g (23%). Purity (hplc) 99%. ¹ H NMR CD ₂ Cl ₂ / δ 7.79 (2K d), 7.47 (2H, d), 7.34 (1H, dd), 7.31 (2H, d),
7.30 (2H, d), 7.02 (1H, d), 2.67 (2H, t), 2.66 (2H, t), 1.66 (4H, qui),
1.37-1.26 (12H, m), 0.91 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2960, 2857, 1613, 1513, 1160, 1038, 910, 838, 8073,
661 MS m / z 474 (M ⁺ ) (100%). 417, 389, 331, 232

[0208] Example 59 6,7-Difluoro-2- (2,3-difluoro-4-heptylphenyl) -5- (4-heptene butylphenyl) benzo [b] Step Preparation of furan (Compound 76 in Table 1) 1 5-bromo-6,7-difluoro-2- (2,3-difluoro-4-heptylphenyl) Baie emission zone [b] furan compound of preparation the title using the following amounts, example 24 ( Prepared and purified by a method similar to that described under 1). 2,3-difluoro-1-iodo-4-heptylbenzene (Example 52 (4)) (2.3 g,
6.7 mmol), 5-bromo-6,7-difluorobenzo [b] furan-2-boric acid (Example 58 (6)) (1.6 g, 5.6 mmol), sodium carbonate (1.8 g, 17.0 mmol), Tetrakis (triethylphosphine) palladium (0) (0.2 g, 0.2 mmol). A white crystalline solid was obtained. Yield: 0.6 g (24%), melting point: 62-65 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.69 (1H, ddd), 7.60 (1H, dd), 7.18 (1H, dd), 7.12 (1H,
ddd), 2.72 (2H, dt), 1.65 (2H, qui), 1.31 (8H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2932, 2856, 1605, 1476, 1210, 1031, 932, 869, 731,
606 MS m / z 444, 442 (M ⁺ ) (100%), 357, 277, 249, 230

[0209] Step 2 6,7-difluoro-2- (2,3-difluoro-4-heptylphenyl) -5- (4-heptene butylphenyl) benzo [b] furan prepared the title (Compound 76 in Table 1) The compound was prepared in a similar manner as described in Example 24 (1) using the following amounts. Product of Step 1 (0.6 g, 1.2 mmol), 4-heptylbenzene boric acid (0.3 g, 1.5 mmo
l), sodium carbonate (0.3 g, 3.0 mmol), tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol). The product is flash chromatography [silica gel / petroleum fraction (boiling point 40-60
C)] and then recrystallization (ethanol). Colorless plate-like crystals were obtained. Yield: 0.1 g (17%). Purity (hplc)> 99%. ¹ H NMR CD ₂ Cl ₂ / δ 7.72 (1H, ddd), 7.47 (2H, dd), 7.40 (1H, dd), 7.30 (2H,
d), 7.25 (1H, dd), 7.12 (1H, ddd), 2.72 (2H, t), 2.67 (2H, t), 1.39-1.62
(4H, m), 1.37-1.28 (16H, m), 0.90 (3H, t), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2928, 2857, 1616, 1475, 1164, 1093, 932, 879, 809, 7
19 MS m / z 538 (M ⁺ ) (100%), 467, 453, 368, 184

[0210] Example 60 Table 1 step Preparation of Compound 77 1 5- (2,3-Difluoro-4-heptyl) -6,7-difluoro-benzo [b] compounds of the tone made title furan, the following amounts Was prepared and purified in the same manner as described in Example 24 (1). 5-Bromo-6,7-difluorobenzo [b] furan (1.1 g, 4.7 mmol), 1-heptyl
-2,3-Difluorobenzene-4-boric acid (1.4 g, 5.6 mmol), sodium carbonate (1.
3 g, 12.0 mmol), tetrakis (triethylphosphine) palladium (0) (0.2
g, 0.2 mmol). After refluxing (1 day), tlc and glc analysis showed that some starting material still remained, so compound 161 (0.6 g, 2.3 mmol) and catalyst (0.1 g, 0.1 mmol).
) Was added. A white crystalline solid was obtained. Yield: 0.8 g (47%), melting point: 57-59.5 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.75 (1H, d), 7.35 (1H, ddd), 7.08 (2H, m), 6.87 (1H, d
d), 2.73 (2H, dt), 1.66 (2H, qui), 1.34 (8H, m), 0.90 (3H, t) IR (KBr) ν _max / cm ^-1 2921, 2859, 1618, 1512, 1121, 1046, 963, 807, 738,
671 MS m / z 364 (M ⁺ ), 335, 279 (100%), 250, 201

Step 2 5- (2,3-Difluoro-4-heptyl) -6,7-difluorobenzo [b] furan-pho
Preparation of uric acid The title compound was prepared using the following amounts of 4'-pentylphenyl boric acid (Example 2
0 (2)) was prepared and purified in a similar manner as described above. Step 1 product (0.7 g, 1.9 mmol), n-butyllithium (2.5 M in hexane, 0.9 m
l, 2.3 mmol), trimethylborate (0.4 g, 3.8 mmol). A white solid was obtained. Yield: 0.1 g (quant). MS m / z 364 (M ⁺ -B (OH) ₂ ), 292, 279 (100%), 250, 121

[0212] Step 3 2- (4-heptyl-phenyl) -5- (2,3-difluoro-4-heptyl) -6,7-diphenyl Ruorobenzo [b] furan (Compound 77) Compound Preparation The title is the following Was prepared and purified in a similar manner as described in Example 24 (1). 1-heptyl-4-iodobenzene (0.7 g, 2.4 mmol), step 2 product (0.8 g, 2.
0 mmol), sodium carbonate (0.6 g, 5.7 mmol). Tetrakis (triethylphosphine) palladium (0) (0.1 g, 0.1 mmol). Final purification was by preparative hplc (acetonitrile / chloroform 4: 1).
A white crystalline solid was obtained. Yield: 0.1 g (5%). Purity (hplc)> 99.9%. ¹ H NMR CD ₂ Cl ₂ / δ 7.80 (2H, d), 7.32 (1H, d), 7.31 (2H, d), 7.13-7.07 (1H
, in), 7.12-7.06 (1H, m), 7.04 (1H, d), 2.73 (2H, dt), 2.67 (2H, t), 1.6
9 (2H, qui), 1.67 (2H, qui), 1.38-1.26 (16H, m), 0.90 (3H, t), 0.89 (3H,
t) IR (KBr) ν _max / cm ^-1 2929, 2859, 1618, 1279, 1053, 969, 908, 835, 811 MS m / z 538 (M ⁺ ) (100%), 453, 416, 368, 290

Example 61 Preparation of Compound 78 in Table 1 Step 1 Preparation of 2,3-difluoro-4-heptylphenol The title compound was prepared as described in Example 58 (2) using the following amounts. Prepared and purified in a similar manner. Hydrogen peroxide (100 vol, 27.0 ml, 238.0 mmol), 1-heptyl-2,3-difluorobenzene-4-boric acid (10.0 g, 39.0 mmol). A colorless liquid was obtained. Yield: 5.9g (66%), Boiling point: 20mmHg, 205 ℃. ¹ H NMR CD ₂ Cl ₂ / δ 6.82 (1H, ddd), 6.69 (1H, ddd), 5.25 (1H, s, br), 2.58
(2H, dt), 1.56 (2H, t), 1.31 (8H, in), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 3390, 2935, 2863, 1643, 1609, 1517, 1183, 1024, 961
, 809, 676 MS m / z 228 (M ⁺ ), 169, 156, 143 (100%), 95

Step 2 2- (2,3-Difluoro-4-heptylphenoxy) acetaldehyde dimethylacetate
Preparation of Cetal The title compound was prepared and purified in a manner similar to that described for the preparation of 2- (4-pentylphenoxy) acetaldehyde dimethyl acetal in Example 25 (1). 2,3-Difluoro-4-heptylphenol (5.8g, 25.0mmol), bromoacetaldehyde dimethyl acetal (5.1g, 30.0mmol), potassium carbonate (6.9g, 50.0mm)
ol), potassium iodide (0.2 g, 1.3 mmol). A colorless oil was obtained which solidified on cooling to a waxy solid. Yield: 5.4g (68%), Boiling point: 170mm at 0.05mmHg. ¹ H NMR CDCl ₃ / δ 6.81 (1H, ddd), 6.67 (1H, ddd), 4.72 (1H, t), 4.05 (2H,
d), 3.47 (6H, s), 2.57 (2H, dt), 1.57 (2H, m), 1.29 (8H, m), 0.88 (3H, t
) IR (KBr) ν _max / cm ^-1 2936, 2863, 1640, 1513, 1176, 1151, 1115, 1095 MS m / z 316 (M ⁺ ), 284, 253, 126, 75 (100%)

Step 3 Preparation of 6,7-difluoro- 5-heptylbenzo [b] furan The title compound was prepared from 5-bromobenzo [b] furan (Example 9 (
Prepared and purified by a method similar to that described in 2). The product of step 2 (5.4 g, 17.0 mmol), polyphosphoric acid (7.3 g). A pale yellow liquid was obtained. Yield: 0.5 g (12%), boiling point: 0.1 mmHg, 135 ° C. ¹ H NMR CD ₂ CI ₂ / δ 7.65 (1H, d), 7.16 (1H, m), 6.76 (1H, dd), 2.72 (2H, dt
), 1.63 (2H, qui), 1.31 (8H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2933, 2867, 1616, 1131, 1077, 926, 871, 763, 733, 551
MS m / z 252 (M ⁺ ), 209, 167 (100%), 153, 118

Step 4 Preparation of 6,7-difluoro-5-heptylbenzo [b] furan-2-boric acid The title compound was prepared as described in Example 20 (2) using the following amounts: Was prepared and purified by the method Step 3 product (0.5 g, 1.8 mmol), n-butyllithium (2.5 M in hexane, 0.8 m
l, 2.0 mmol), trimethylborate (0.4 g, 3.6 mmol). An orange solid was obtained. Yield: 0.3 g (66%). MS m / z 252 (M ⁺ ), 180, 167 (100%), 119, 57

Step 5 Preparation of 4-Bromo-3-fluoro-4′-pentylbiphenyl The title compound was prepared and purified in a similar manner as described in Example 24 (1) using the following amounts: did. 1-Bromo-2-fluoro-4-iodobenzene (6.4 g, 21.0 mmol), 4-pentylbenzene boric acid (Example 3 (2)) (4.5 g, 23.0 mmol), sodium carbonate (5.6 g, 53)
.0 mmol), tetrakis (triethylphosphine) palladium (0) (1.2 g, 1.0 mmol
). A pale yellow liquid was obtained. Yield: 1.7 g (25%) (spilled less), Boiling point: 0.04 mmHg, 190 ° C. ¹ H NMR CD ₂ Cl ₂ / δ 7.60 (1H, dd), 7.49 (2H, d), 7.37 (1H, dd), 7.29 (1H, d
d), 7.28 (2H, d), 2.65 (2H, t), 1.64 (2H, qui), 1.35 (4H, m), 0.91 (3H,
t) IR (KBr) ν _max / cm ^-1 2933, 2861, 1560, 1195, 1057, 875, 805, 547 MS m / z 322,320 (M ⁺ ), 263, 250, 183 (100%), 170

[0218] Step 6 2- (2-fluoro-4'-pentyl-biphenyl) -6,7-difluoro-5 Hepuchirube emission zone [b] furan (Compound 78) Compound Preparation The title uses the following amounts And was prepared and purified in the same manner as described in Example 24 (1). Step 5 product (03.5 g, 1.4 mmol), Step 4 product (0.3 g, 1.2 mmol), sodium carbonate (0.4 g, 3.5 mmol), tetrakis (triethylphosphine) palladium (
0) (0.1 g, 0.1 mmol). Final purification was by preparative hplc (acetonitrile / chloroform 4: 1).
A white solid was obtained. Yield: 0.04 g (7%). Purity (hplc)> 99.2%. ¹ H NMR CD ₂ Cl ₂ / δ 8.07 (1H, dd), 7.58 (2H, d), 7.55 (1H, dd), 7.45 (1H, d
d), 7.30 (2K, d), 7.21-7.19 (1H, m), 7.19-7.17 (1H, m), 2.75 (2H, dt), 2
.66 (2H, t), 1.68-1.64 (4H, m), 1.37-1.26 (12H, m), 0.91 (3H, t), 0.89 (
3H, t) IR (KBr) ν _max / cm ^-1 2925, 2855, 1614, 1556, 1110, 1062, 915, 866, 800 MS m / z 492 (M ⁺ ) (100%), 435, 407, 350 , 175

Example 62 Preparation Step 1 of Compound 1 in Table 1 Preparation of 1 -bromo-4-octyloxybenzene p-Bromophenol (40.0 g, 231 mmol), n-octyl bromide (50.2 g, 260 mmol)
), Potassium carbonate (35.9 g, 260 mmol) and potassium iodide (2.2 g, 13 mmol) in butanone (500 ml) was refluxed under nitrogen (48 h) and the reaction was monitored by glc analysis. The mixture was filtered and the solid washed with ether (2 x 300 ml). The filtrate was washed with sodium hydroxide (10%) then brine. The solvent was removed in vacuo and the product was purified by distillation. A colorless liquid was obtained. Yield: 61.0g (93%), Boiling point: 145 ° C at 0.02mmHg. ¹ H NMR CDCl ₃ / δ 7.35 (2H, d), 6.76 (2H, d), 3.90 (2H, t), 1.76 (2H, qui)
, 1.35 (10H, m), 0.89 (3H, t) IR (KBr) ν _max / cm ^-1 2900, 1580, 1475, 1240, 1170, 1070, 820, 640, 500
MS m / z 286,284 (M ⁺ ), 171 (100%), 157, 143, 93

Step 2 Preparation of 2 -methyl-4-octyloxyphenyl) but-3-yn-2-ol The product of Step 1 (61.0 g, 214 mmol), tetrakis (triethylphosphine) palladium (0) (2.4 g , 2.1 mmol), cuprous iodide (0.4 g, 2.1 mmol) and dry diisopropylamine (400 ml) were stirred under nitrogen (10 min). 2-Methyl-but-3-yn-2-ol (45.0 g, 535 mm) in dry diisopropylamine (90 ml)
ol) was added dropwise and the mixture was brought to reflux (4 h); the reaction progress was monitored by tlc analysis. Upon cooling, water was added, the mixture was filtered through a pad of'Hyflo Supercel 'and the pad was washed with ether. The separated aqueous layer was washed with ether (2 × 300 ml), the combined organic layers were washed with brine and dried (MgSO ₄ ). After removing the solvent in vacuo, the product was purified by flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C) (unreacted starting material), and DCM (product)]. A dull brown oil was obtained. Yield: 33.2 g (54%). ¹ H NMR CDCl ₃ / δ 7.33 (2H, d), 6.81 (2H, d), 3.93 (2H, t), 1.76 (2H, qui)
, 1.60 (6H, s), 1.28 (12H, m), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 3440, 2880, 1600, 1505, 1465, 1370, 1245, 960, 835
MS m / z 288,286 (M ⁺ ), 273, 175,159, 43 (100%)

Step 3 Preparation of 4-octyloxyphenylacetylene Stir the product of Step 2 (33.0 g, 115 mmol) and potassium hydroxide (250 ml) (7.1 g, 126 mmol) in toluene using the Dean and Stark apparatus. While refluxing under nitrogen (3.5 hours). Analysis showed the reaction was complete. The cooled reaction mixture was poured into water (150 ml) and the layers separated. The aqueous phase was neutralized to pH 7 with hydrochloric acid (0.02M) and washed with ether (3 x 100ml). The mixed organic layer was washed with brine and dried (Mg
SO ⁴ ). After removing the solvent in vacuo, the residue was purified by flash chromatography [silica gel / petroleum fraction (bp 40-60 ° C.), DCM 1: 1]. The product was vacuum distilled. A pale yellow liquid was obtained. Yield: 6.4g (68%), Boiling point: 2.7mmHg, 122 ° C. ¹ H NMR CDCl ₃ / δ 7.42 (2H, d), 6.82 (2H, d), 3.94 (2H, t), 3.00 (1H, s),
1.77 (2H, qui), 1.35 (10H, m), 0.88 (3, t) IR (KBr) ν _max / cm ^-1 3310, 3290, 2920, 2850, 2110, 1600, 1500, 830 MS m / z 230 (M ⁺ ), 187, 145, 1118 (100%), 101

Step 4 Preparation of 4,6- diiodoresorcinol To resorcinol (5.0 g, 45 mmol) in hydrochloric acid (concentrated) / water 14:11 v / v (185 ml),
Iodine monochloride (14.6 g, 90 mmol) was added with stirring under nitrogen. Continue stirring (1
5 min), solid sodium sulfite was added until the iodine color disappeared. The reaction mixture was filtered and the solid washed with cold water. The solid was dried in vacuo (KOH), and recrystallized (CCl _4). A colorless needle was obtained. Yield: 8.6 g (53%), melting point: 139-145 ° C (lit. ⁴ 145 ° C). ¹ H NMR DMSO-d ⁶ / δ 9.55 (2H, s), 7.57 (1H, s), 6.53 (1H, s) IR (KBr) ν _max / cm ^-1 3455, 1565, 1285, 1150, 1030, 875 , 630, 460 MS m / z 362 (M ⁺ ), 235, 108, 79, 50 (100%)

Step 5 Preparation of 4,6-diiodresorcinol dibenzoate ester The product of step 4 (15.0 g, 42 mmol) and benzoyl chloride (12.8 ml) in DCM (150 ml).
g, 91 mmol) to a stirred mixture, excluding water, and dried triethylamine (9.2 g, 9 mmol).
1 mmol) was added dropwise and the mixture was refluxed (2 hours). Upon cooling, the mixture was poured into water and washed with DCM (2x200ml). Hydrochloric acid (0.1M) in the mixed organic phase
And washed with water, dried (MgSO _4). The solvent was removed in vacuo and the residue was recrystallized (toluene). White fibrous crystals were obtained. Yield: 20.6 g (86%), melting point: 185-7 ° C (lit. ⁴ 195-200 ° C (decomposition)) ¹ H NMR CDCl ₃ / δ 8.36 (1H, s), 8.26 (4H, d), 7.68 ( 2H, t), 7.54 (4H, t),
7.31 (1H, s) IR (KBr) ν _max / cm ^-1 1745, 1235, 1150, 1050, 700 MS m / z 570 (M ⁺ ), 443, 127 (100%), 105, 77

Step 6 2- (4-octyloxyphenyl) -5- (4-octyloxyphenylethynyl)
Preparation of Benzo [b] furan-6-benzoate Ester (Compound 1) The product of Step 3 (0.7 g, 3 mmol) was placed in a three necked flask equipped with septum, condenser, thermometer and addition funnel. The apparatus was heated and flushed with nitrogen. Dry TH
F (10 ml) was added and the system was degassed at -40 ° C. Flush the flask with nitrogen and reduce the temperature to 0.
N-Butyllithium (1.4 ml, 3.5 mmol, 2 in hexane 2
.5M) was added drop by drop. Stir the mixture at this temperature (15 minutes) and cool the system (
-40 ° C.), anhydrous zinc chloride (0.5 g, 3.5 mmol) in dry THF (20 ml) was added dropwise with stirring. The mixture was allowed to come to room temperature with stirring. Step 5 product (0.
7 g, 1.2 mmol) and tetrakis (triethylphosphine) palladium (0) (0.1 g
, 0.1 mmol) was added and the mixture was refluxed with stirring under nitrogen. The mixture was cooled when tlc analysis showed no further reaction (3 days). The solvent was removed in vacuo and the residue was triturated with ether to precipitate a white solid. The solid was kneaded with a petroleum fraction (bp 40-60 ° C) from a solution in methanol and finally recrystallized (ethanol). Light yellow crystals were obtained. Yield: 0.1 g (14%). Purity (hplc)> 98%. ¹ H NMR CDCl ₃ / δ 8.34 (2H, d), 7.77 (2H, d), 7.74 (1H, s), 7.67 (1H, t),
7.53 (2H, t), 7.47 (1H, s), 7.09 (2H, d), 6.97 (2H, d), 6.86 (1H, d), 6.6
9 (2H, d), 4.20 (2H, t) 3.90 (2H, t), 1.78 (4H, m), 1.30 (20H, m), 0.89
(3H, t), 0.88 (3H, t) IR (KBr) ν _max / cm ^-1 2920, 2850,1735, 1500, 830 MS m / z 671 (M ⁺ ), 566, 446, 3411, 105 (100 %)

Example 63 Liquid Crystal Properties The liquid crystal properties of the present invention were tested using conventional methods. Examples of metastases are given in the examples above. However, the results are summarized in Table 3 below.

[Table 10]

[0226]

[Table 11]

[0227]

[Table 12]

[0228]

[Table 13]

Example 64 Liquid Crystal Properties of Mixtures Containing Compounds of the Invention Many mixtures were prepared by adding a given proportion of a compound of the invention to a conventional host mixture containing ethyl-linked phenylcyclohexane. The properties of the mixture were analyzed using conventional methods and the results are shown in Tables 4-7 below.

[0230]

[Table 14]

[0231]

[Table 15]

This data gives some indication of the structural effects on properties.
For example, the effect of fluorine substituents can be evaluated by comparing the properties of Mixtures 7 and 8 and 9 and 16. When fluorine is present on the remote ring (compound 82 for each)
Mixtures 8 and 9 containing 31 and 31), a smectic phase is observed, but when they are on the benzofuran central ring (as in Mixture 7 containing compound 38) only the nematic phase is observed. The transition temperature for fluorinated compounds is
Significantly low compared to the corresponding non-fluorinated compound.

[0233]

[Table 16]

[0234]

[Table 17]

From the comparison of Mixtures 1, 2 and 14, ε is obtained when the nitrile is a substituent on the phenyl ring rather than the furyl ring of benzofuran (ie R ¹ is cyano rather than R ³ ). ⊥ seems to be large. This may also be responsible for the increase in Δε (from 7.8 to 8.7).

[0236]

[Table 18]

[0237]

[Table 19] * Base compound of ethyl-linked phenylcyclohexane without the compound of the invention.

The properties of the ester-containing compounds can be compared by comparing mixtures 4, 5 and 12 and the results below. The properties of the tricyclic system can be evaluated in relation to each other by comparing the results of the examples obtained with mixtures 1, 10 and 15. This indicates that the relative position of the benzofuran ring with respect to the phenyl ring in the system has a considerable effect on the dielectric anisotropy. A comparison of the results of Mixtures 1, 2, 11 and 14 shows that the position of the cyano groups on the different rings of the benzofuran ring does not appreciably affect the birefringence. However, a comparison of the tricyclic systems 1, 10 and 15 shows that the birefringence of the mixture is lower when the benzofuran moiety belongs within the central phenyl ring and is far from the cyano substituent.

The influence of other groups such as pyrimidines, triple bonds and chiral moieties can be assessed by the results obtained with eg mixtures 3, 6 and 13. The 5% mixture was used in some tests as compound 37 in mixture 6 tends to precipitate out of solution.
Compound 17 was less stable than some other compounds.

Each mixture was filled into a 6 μm TN cell with a worn polyimide alignment layer and 5
The optical switching time at 25 ° C., 40 ° C. and (T _NI −30) ° C. by applying Vpk-pk 1 KHz square was wave-measured. The results are shown in Table 7 below, along with measurements of a mixture of ethyl-linked phenylcyclohexane without the compound of the invention in the cell from the same batch.
Shown in.

[0241]

[Table 20]

[0242]

[Table 21]

Switching rates indicate that the compounds of the invention have low switching viscosities. Looking at the switching times at reduced temperature (T _NI −30) ° C. (shown in bold in Table 7), these are generally much faster than in pure compounds. This seems to be the case even when terphenyl and negative substances are added.

Example 65 Comparison of a mixture of compounds of the invention with a cyanobiphenyl compound of formula A:

[Chemical 28] Where a eutectic mixture of the corresponding cyanobiphenyls, where R is propyl- (C3), pentyl- (C5) and heptyl (C7), and an equivalent eutectic mixture of propyl-, pentyl- and heptylphenylbenzofuran ( (As calculated by the Schroeder van Laar equation) and the results are shown in Tables 8-10 below.

[0245]

[Table 22] Table 8 gives the phase behavior and the composition of the mixture. The benzofuran mixture has a clearing point above 15 ° higher than cyanobiphenyl. Neither mixture recrystallized when held at -40 ° C for 40 minutes, but if held at this temperature for a sufficiently long time, both will probably recrystallize.

[0246]

[Table 23] These results show that the birefringence of the compounds of the invention is as high as the dielectric anisotropy.

[0247]

[Table 24]

The liquid crystal properties of the mixtures containing the compounds of the invention were compared with similar mixtures, using the corresponding compounds in which the benzofuran ring was replaced by phenyl rings. The results are shown in Table 11.

[0249]

[Table 25]

[0250]

[Table 26]

These results indicate that, in general, the compounds of the present invention have a wider nematic phase range than equivalent biphenyl compounds. (This range is slightly narrower for the terphenyl equivalent).

Example 66 Liquid Crystal Properties of Fluoro-to-Non-Fluoro Compound Mixtures of the Invention The phase behavior and structure of mixtures of compounds of the invention including difluoro compounds and some of the mixtures defined in Table 11 were determined.

[0253]

[Table 27] The compounds of the present invention may have a wider nematic phase range than the equivalent biphenyl compounds.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C07D 405/04 C07D 405/04 C09K 19/34 C09K 19/34 G02F 1/13 500 G02F 1/13 500 ( 81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), GB, JP, US (72) Inventor Toin Kennis Johnson United Kingdom Hull H.U. 6 7 Rx University of Hall School of Chemistry (No Address) (72) Inventor Hard Michael United Kingdom Hull H.U. 6 7 Rx University of Hull School Of chemistry (No address) (72) Inventor Friedman Mark Richard United Kingdom Hull HI 6 7 Rx University of Hall School of Chemistry (No address) (72) Inventor Jones John Clifford United Kingdom Walks W 14 W3 Morvern St Andrews Road Dela Morvan (No Address) F Term (Reference) 4C037 PA02 QA06 QA11 QA12 QA13 QA20 4C063 AA01 BB01 CC76 DD29 EE10 4H027 BA01 DL01 DL02 DL03 DL05

Claims (26)

[Claims] 1. A liquid crystal compound of the following general formula (I), wherein: Wherein X is O, S or Se and each R ¹ and R ³ is independently cyano, halo, optionally substituted hydrocarbyl, optionally substituted alkoxy, optionally substituted heterocycle, group R ¹³ C (O) O-, wherein R ¹³ is selected from optionally substituted hydrocarbyl or carboxy or hydrocarbyl ester or amide thereof, provided that at least one or the group R ¹ or R ³ is cyano or Other than halo, each R ² and R ⁴ is independently halo, nitro, lower alkyl optionally substituted with halo,
Or a group R ¹⁴ C (O) O −, wherein R ¹⁴ is an optionally substituted hydrocarbyl, n is 1 or 2, m is 0, 1, 2 or 3, p is 1 or 2, and q is 0 or 1, provided that n + m does not exceed 4 and p + q does not exceed 2, and the compound is other than the compound represented by the following formula (A) or (B). Liquid crystal compound on condition: In the formula, R ¹¹ is a C _1-8 alkyl group; R ¹² is H, or a C _1-12 alkyl group or a C _2-12 alkenyl group, both of which are optionally CN or CF ₃ groups or one May be substituted with the above halogen atoms;
And one or more —CH ₂ — groups in the alkyl or alkenyl group are optionally —O—, —S
-, -C (O)-, -OC (O)-or -OC (O) O-, provided that the oxygen and sulfur atoms are not directly bonded to each other; A'and A "are independent Selected from: a) a trans-1,4-cyclohexylene residue, in which one or more non-adjacent CH ₂ groups can be replaced by —O— and / or —S—; b) 1, 4-cyclohexenyl residue; c) 1,4-phenylene residue, in which one or more CH groups can be replaced by N; d) group 1,4-bicyclo (2,2,2) -octylene , A residue derived from piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetra-hydronaphthalene-2,6-diyl; Thereby, the residues a), b) and c) can be replaced by CN, Cl or F and Z ″ and Z ′ ″ are independently —C (O) O—, — OC (O) -, - CH 2 O -, - OCH _2- , -C
H ₂ CH _2- , -CH = CH-, -C≡C- or a single bond, and g is 0, 1 or 2, and Wherein each Ar is optionally substituted with C _1-4 alkyl, fluoro, chloro, bromo, cyano, or hydroxy, and is optionally one or more —O—, —S—, —NH—, —NR. ^c-
, -COO-, -OCO-, OCOO or CO is a bond or spacer group such as a C _2-30 alkylene or C _2-30 alkenylene group; each M is independently optionally substituted. aliphatic, aromatic, selected from heteroaliphatic or heteroaromatic ring system, X is, O, a S, COO, OCOO, CONH or CONR ^c, R ^c is located at C _1-4 alkyl; e and f are independently selected from 0, 1 or 2 and each Y ′ group is independently O, S, COO, OCOO, CONH, NHCO, CONR ^c or NR ^c CO, where R ^c is As defined above; each Z ′ group is independently selected from hydrogen, cyano or a polymerizable group. 2. The compound according to claim 1, wherein n is 1 and m is 0 or 1. 3. At least one of R ¹ and R ² is fluoro.
The compound according to. 4. One of R ¹ or R ³ is cyano or halo and the other is
Is an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted aryl, an optionally substituted heterocycle, carboxy or an ester thereof. The compound according to any one of claims 1 to 3. 5. R ¹ or R ³ other than cyano or halo is represented by the following formulas (i) and (ii)
, (Iii), (iv), (v), (vi), (vii) or (viii) group, [Chemical 5] Wherein X is 0 or 1, R ¹⁰ is a C _1-20 alkyl group, and y and z are independently selected from 0, 1 or 2. 5. The compound according to. 6. A compound of the following general formula (IA): Wherein X is oxygen, sulfur or cerium, R ^1a and R ^1b are independently hydrogen, cyano, halo, optionally substituted hydrocarbyl, optionally substituted heterocycle or carboxy or hydrocarbyl ester or amide thereof. Selected from
Provided that at least one group R ^1a or R ^1b is other than hydrogen; one of R ¹⁷ or R ¹⁸ is cyano, halo, optionally substituted hydrocarbyl, optionally substituted heterocycle or carboxy or hydrocarbyl ester or The amide and, on the other hand, hydrogen, halo, nitro, lower alkyl optionally substituted with halo, or the group R ¹⁵ C (O) O-, wherein R ¹⁵ is an optionally substituted hydrocarbyl group. R ^2a and R ^2b are independently hydrogen, halo, nitro, lower alkyl optionally substituted with halo, or the group R ¹⁴ C (O) O—, where R ¹⁴ is as defined above. Selected; provided that: (i) at least one group R ^1a or R ^1b or R ¹⁷ or R ¹⁸ is other than cyano or halo; (ii) when X is S, R ¹⁷ is a carboxy or hydrocarbyl ester or That net In and, R ¹⁸ is hydrogen, R ^2a and R ^2b are both not fluoro; if (iii) X is O, R ¹ is an optionally substituted hydrocarbyl or carboxy or hydrocarbyl ester or amide thereof , R ^2a is hydrogen, R ^1b and R ^2b are both fluorine, and R ¹⁷ is other than C _1-8 alkyl. 7. One of R ^1a or R ^1b or R ¹⁷ or R ¹⁸ of formula (IA) is cyano or halo and at least one of said groups on the other ring of the bicyclic ring in (IA) 1
Are optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted aryl, optionally substituted heterocycle, carboxy or hydrocarbyl thereof. The compound according to claim 6, which is an ester. 8. A compound according to claim 1 of formula (II): Wherein R ⁵ is a group R ^{3 as} defined in claim 1 above, one of R ⁷ and R ⁸ is a group R ^{1 as} defined in claim 1 and the other is hydrogen or A group R ^{1 as} defined in claim 1; R ⁶ is hydrogen, cyano or fluoro, R ⁹ is hydrogen, cyano or fluoro, provided that R ⁵ is cyano or fluoro; ^At least one of ⁷ and R ⁸ is an optionally substituted alkyl, an optionally substituted cycloalkyl, an optionally substituted alkenyl, an optionally substituted alkynyl, an optionally substituted alkoxy, an optionally substituted Aryl, optionally substituted heterocycle, carboxy or an ester thereof; and when one of R ⁷ or R ⁸ is cyano or fluoro and the other is hydrogen, then R ⁵ is optionally substituted alkyl. , Arbitrarily replaced Alkenyl, optionally substituted substituted alkynyl, optionally alkoxy, optionally substituted aryl, heterocycle optionally substituted, a carboxy or an ester thereof. 9. A compound according to claim 8 of formula (IIA): Wherein R ^{5 ′} is cyano or fluoro, preferably fluoro, one of R ^{7 ′} and R ^{8 ′} is hydrogen, and the other is an optionally substituted hydrocarbyl group or a heterocyclic group as described above. is there. 10. At least one of R ^{7 ′} or R ^{8 ′} is a group of sub-formula (i), (ii), (iii), (vi) or (viii) as defined in claim 5. 10. The compound according to claim 9. 11. The liquid crystal compound according to claim 1, wherein X is oxygen. 12. A liquid crystal compound according to claim 8 comprising a compound of formula (II) wherein R ⁶ is hydrogen or fluoro and R ⁹ is hydrogen or fluoro. 13. A liquid crystal mixture containing the compound according to claim 1. 14. A liquid crystal mixture according to claim 13, comprising at least two different compounds according to any one of claims 1-12. 15. A liquid crystal display device (LCD) comprising a compound according to any one of claims 1 to 12 or a mixture according to claim 13 or 14.
Liquid crystal device like. 16. A liquid crystal compound according to any one of claims 1 to 12 or a mixture according to claim 13 or 14 having electroclinic properties. 17. An electroclinic device comprising the liquid crystal compound or mixture according to claim 16. 18. A liquid crystal compound according to any one of claims 1 to 12 or a mixture according to claim 13 or 14, which has cholesteric properties. 19. A device comprising a liquid crystal compound or mixture according to claim 18, wherein the device is a thermoptic, thermographic or electro-optical device. 20. A liquid crystal compound according to any one of claims 1 to 12 or a mixture according to claim 13 or 14, which has ferroelectric properties. 21. A ferroelectric device comprising the liquid crystal compound or mixture according to claim 20. 22. A liquid crystal compound according to any one of claims 1 to 12 or a mixture according to claim 13 or 14, which has flexo-electrical properties. 23. A flexo-electrical device comprising a liquid crystal compound or mixture according to claim 22. 24. A pyroelectric property according to claim 1, which has pyroelectric properties.
15. The liquid crystal compound according to item 13 or the mixture according to claim 13 or 14. 25. A pyroelectric device comprising a liquid crystal compound or mixture according to claim 24. 26. A method for preparing a compound of formula (I) according to claim 1, comprising:
A method comprising any of the following steps: (i) a compound of formula (III): Wherein R ² , R ³ , R ⁴ , X, n, m, p and q are as defined in claim 1,
And Z is a leaving group or a group B (OH) ₂ is a compound of formula (IV) below, wherein R′-Z ′ (IV), wherein R ¹ is as defined for formula (I) And Z ′ is a group B (OH) ₂ when Z is a leaving group, or a compound which is a leaving group when Z is B (OH) ₂ ; or (Ii) a compound of the following formula (V): Wherein R ¹ , R ² , R ⁴ , X, n, m, p and q are as defined for formula (I) and Z is a compound as defined for formula (III). , The following formula (VI)
A compound of R ³ -Z ′ (VI), wherein R ³ is as defined for formula (I) and Z ′ is as defined for formula (IV) Or (iii) when q is 0, p is 1 and R ³ is a carboxy group, the following formula (IX)
A compound of ^{Wherein, R 2, R 4, X} , m, n and q are as defined for formula (I), and R ^{1 'is} R ¹ or a precursor thereof, as defined for formula (I) Carboxylating a compound which is a carboxylating agent and then acidifying the product with an acid such as glacial acetic acid; or (iv) when q is 0, a compound of formula (XIII) Yes, [Chemical formula 12] In the formula, R ^{1 ′} , R ² , X, n and m are compounds represented by the following formula (XIV)
HO ₂ C—R ^{3 ′} (XIV), wherein R ^{3 ′} is reacted with a compound which is a group R ^{3 as} defined for formula (I) or a precursor thereof, and then, if necessary, For example, the step of converting any of the groups R ¹ , R ² , R ³ or R ^{4 into} a different such group.