JPH03284673A - Thiophene derivative - Google Patents

Abstract

NEW MATERIAL:A compound of the formula (X is H or CHO; Y is CH=CHOR, CH=CHOH or CH2CHO; R is 1-8C alkyl). EXAMPLE:2-(2-Methoxyvinyl)thiophene. USE:Useful as an intermediate for synthesizing polymers, oligomers, pesticides and medicines, functional materials such as electronic materials, coloring matters such as cyanine-based ones, etc. PREPARATION:The objective compound of the formula (where, X is H) can be obtained by reaction at 0-150 deg.C in a solvent such as methanol in the presence of a base (e.g. potassium t-butoxide) between 2-thiophenealdehyde and a phosphonium compound. The amounts of the reactants to be used are 1-10mols and 1-10mols for the phosphonium compound and base, respectively (each per mol of 2-thiophenealdehyde).

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to novel thiophene derivatives.

[Conventional technology]

Thiophene is widely used as a solvent and as a synthetic raw material for polymers, dyes, pharmaceutical and agricultural products, and the like. Various kinds of thiophene derivatives such as thiophene aldehyde and thiophenecarboxylic acid are known, but a thiophene derivative represented by the general formula (1) described below is not known.

[Problem to be solved by the invention]

An object of the present invention is to provide a novel thiophene derivative useful as a synthetic intermediate for polymers, oligomers, medical and agricultural products, functional materials such as electronic materials, and pigments such as cyanine dyes.

[Means to solve the problem]

The present invention relates to the following thiophene derivatives.

(1) A thiophene derivative represented by the following -line formula [1].

(In the formula, X is a hydrogen atom or -CH0 group, Y is -CH=
C++OR group, -CH=CHOH group or -C)12C
Indicates HO group.

Here, R represents an alkyl group having 1 to 8 carbon atoms. )(2)
The thiophene derivative according to (1) above, wherein X is a hydrogen atom and Y is a -CH═CH0CH□ group.

(3) x is -CHO group, Y is -CH=C)IOC
The thiophene derivative according to (1) above, which has a H group.

In the present invention, a compound in which the substituent represented by Y in the above-mentioned -line formula [l] is a -CH=CHOR group is used as a thiophene derivative A.
, -CII=CHOH group is called thiophene derivative B, and a compound where -CH2CJIO group is called thiophene derivative C.

Examples of the alkyl group represented by R in the thiophene derivative A include linear or branched carbon atoms having 1 to 8 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, and octyl group. I can give you something like this.

Thiophene derivative A or B may have geometric isomers due to double bonds within the molecule. Therefore, the thiophene derivative A or B exists in the form of a cis isomer, a trans isomer, or a mixture thereof, and can be mutually converted depending on conditions such as temperature.

Thiophene derivatives B and C are hydrolysates of thiophene derivative A, and these are mutually ke-1-enol tautomeric isomers and can be converted into each other depending on conditions such as temperature and solvent.

The thiophene derivative A of the above-mentioned -line formula (1) in which X is a hydrogen atom can be synthesized from 2-thiophene aldehyde through a Wittig reaction. Therefore, it can be synthesized, for example, by reacting 2-thiophene aldehyde and a phosphonium compound in the presence of a base.

Examples of the above phosphonium compounds include (Chp”c
o20CH3Br-1 ((topp"c++, oco, L, etc.) can be mentioned.

Examples of the base include (C1+3)3COK, CH
3O) 12CH20 = CH, CH2O, etc. can be given.

Thiophene derivative A in which X is a hydrogen atom by the above method
To synthesize 2-thiophene aldehyde, and 1
1 to 10 moles, preferably ~1.5 moles of a phosphonium compound per mole of 2-thiophene aldehyde;
1 to 10 mol, preferably J to 1.5 mol of base,
in the reaction medium under a pressure of 0 to 10 kg/cffl-G, preferably 0 to 5 kg/d-G, at a temperature of 0 to 150°C, preferably 25 to 100°C, for 0.1 to 100 hours.
Preferably, it can be carried out by reacting for J to 50 hours. Examples of the reaction medium used at this time include alcohols such as methanol, ethanol, isopropanol, n-butanol, and 2-methyl-2-propanol.

When methoxymethyltriphenylphosphonium bromide is used as the phosphonium compound and potassium tert-butoxide is used as the base, the reaction can be expressed by the following reaction formula. 3 After the reaction is complete, remove the solvent using ethyl ether, chloroform, etc. After extraction, the desired thiophene derivative A in which X is a hydrogen atom can be obtained by removing the solvent using a method such as vacuum distillation.

Furthermore, if necessary, a purified product of higher purity can be obtained by a method such as chromatography.

The phosphonium compound is a halogenated methyl alkyl ether (ROCI (2X), where R is the same as in the above-mentioned -line formula [1], and X is a halogen atom).

) can be synthesized by reacting.

The thiophene derivative A in which X in the -line formula [■] is a -CHO group can be synthesized by formylating the thiophene derivative A obtained above in which X is a hydrogen atom. Therefore, for example, a thiophene derivative in which X is a hydrogen atom can be synthesized by reacting an alkyllithium such as butyllithium with N,N-dimethylformamide. To explain a preferable method for synthesizing thiophene derivative A, first, thiophene derivative A in which X is a hydrogen atom is added in a reaction medium to 1 to 5
mol, preferably 1 to 2 mol of alkyl lithium is added under water cooling, and after addition it is heated under a pressure of 0 to 10 kg/cd-6, preferably 0 to 5 kg/cd-6, at 0 to 100°C, preferably 0 React at a temperature of ~50°C for 0.01 to 10 hours, preferably 0.02 to 1 hour, and then add ~5 mol to the reaction solution of thiophene derivative A] where X is a hydrogen atom] Preferably 1 to 2 moles of N.

N = Nidimethylformamide Added under water cooling, O after addition
~lokg/cd-G, preferably O~5kg/cJ-
Under the pressure of G, 0-150℃, preferably 0-100℃
at a temperature of 0.0] to 10 hours, preferably 0.02 to
Let react for 1 hour. The reaction medium used at this time is
Examples include ethers such as ethyl ether and propyl ether.

The reaction formula when the thiophene derivative A in which X is a hydrogen atom is reacted with butyllithium and then reacted with ~,N-dimethylformamide can be represented by the following reaction formula.

(In the formula, R is the same as in the above-mentioned -line formula [1), and Bυ represents a butyl group. ) After the reaction is completed, thiophene derivative A where X is a hydrogen atom
The desired thiophene derivative A in which X is -CIIO group can be obtained in the same manner as in the case of .

Thiophene derivative B or C can be obtained by hydrolyzing thiophene derivative A in the presence of an acid catalyst. That is, when thiophene derivative A where X is a hydrogen atom is hydrolyzed, thiophene derivative B or C where X is a hydrogen atom is obtained, and when thiophene derivative A where X is a -CHO group is hydrolyzed, X is -CIIO. The radical thiophene derivative B or C is obtained.

The thiophene derivative of the present invention represented by the above-mentioned -line formula (1) can be used as a synthetic intermediate for polymers, oligomers, medical and agricultural products, functional materials such as electronic materials, and dyes such as cyanine dyes.

Thiophene derivative A is easily hydrolyzed and converted into thiophene derivative B or C in the presence of an acid catalyst. For this reason, thiophene derivative B or C may be generated during the synthesis of thiophene derivatives, but the generated thiophene derivative B should not be separated from thiophene derivative A and should be used as a mixture with thiophene derivative A as a synthetic intermediate. I can do it. On the other hand, after converting the thiophene derivative C into the thiophene derivative 3, the mixture can be used as the synthetic intermediate.

[Effects of the Invention] According to the present invention, a thiophene derivative is obtained which is novel and useful as a synthetic intermediate for polymer oligomers, medical and agricultural products, functional materials such as electronic materials, and pigments such as cyanine dyes.

〔Example〕

Next, examples and reference examples of the present invention will be described.

Example] (Synthesis of methoxymethyltriphenylphosphonium bromide) After dissolving 105 g (0.40 moR) of triphenylphosphine ((C,l-1,)3P) in 30 (lcQ) of toluene, 50 g of methoxymethyltriphenylphosphonium bromide was dissolved under ice cooling. (0,40moQ) of bromomethyl methyl ether (CH30CH2Br)
It was added dropwise over a period of minutes. Thereafter, this solution was stirred at room temperature for 24 hours, and then separated into solid and liquid by filtration. The obtained solid was washed several times with acetone and then dried to obtain 145 g of a white solid of methoxymethyltriphenylphosphonium bromide ((C1(,),P"CH,0CI(,Br-) (yield: 93 .8mof)%).

(Synthesis of 2-(2-methoxyvinyl)thiophene)8.
2g (73mmo(Rino 2-thiophene aldehyde <M
”> and 35 g (90,4 secondary ions) of the above methoxymethyltriphenylphosphonium puromite at 300
To this, 8.64 g (77+n+noU) of potassium te
rt-butoxide ((C1+3), C0K) at 15
A solution dissolved in 0 ml of 2-methyl-2-propanol was added dropwise at room temperature over 30 minutes.

Thereafter, this reaction solution was heated to 70° C. and stirred for 24 hours.

Next, the reaction solution was made alkaline by adding saturated sodium hydrogen carbonate solution and extracted with 200 mL of ethyl ether three times.Then, it was washed with saturated brine, and then anhydrous sodium sulfate was added. The solution was dried by distillation under reduced pressure to remove ethyl ether and concentrated.

Next, this concentrated solution was applied to a silica gel column (Wakogel C-
200 (manufactured by Wako Pure Chemical Industries, Ltd., trade name) and a developing solvent (hexane:ethyl acetate = 2:1, volume ratio) to obtain 9.5 g of a yellow transparent liquid.

"HNMR spectrum (solvent two CDC) of the obtained compound
ρ3, reference material: tetramethylsilane, equipment (JEOL
GX-270 (manufactured by JEOL Ltd.): 270 MHz) and mass spectra (electron impact ionization method), this compound is 2-(2-methoxyvinyl)thiophene (fifCH"CH- molecular weight 140). ”)l NMI (The results of the spectrum and mass spectrum are as follows.

18 NMR spectrum δ:=3.58.3.74 (3H,s, 2 peak
s) 5.65 to 7.28 (5H, m) Mass spectrum m/Z = 140 The other fractions separated during separation and purification of the concentrate using a silica gel column were 2-(2-methoxyvinyl)thiophene 2-hydroxyvinylthiophene (mass spectrum: m/Z=126), which is a hydrolyzate of
-Formylmethylthiophene (mass spectrum: m/
Z = 126).

Example 2 (Synthesis of 2-(2-methoxyvinyl)-5-thiophene aldehyde) 9.5 g (67,9 mmoQ) of 2-(2-methoxyvinyl)thiophene was dried with molecular sieves.
After dissolving in mQ of ethyl ether, 65II was added under water cooling.
A hexane solution of 1.57M butyllithium (102.1i+moQ as butyllithium) of I□Q was added dropwise over 5 minutes. After the dropwise addition was completed, the temperature of the reaction solution was raised to 20°C.
Stirred for 30 minutes.

Next, this reaction solution was dried with molecular sieves.
m1Q N,N-dimethylformamide and 20 itfl
was added dropwise to the mixture with ethyl ether over 10 minutes while cooling with water. After the dropwise addition, the temperature of this reaction solution was raised to 20°C, and 1
Stir for 5 minutes.

Next, 20 mQ of saturated sodium bicarbonate water was added to the reaction solution to stop the reaction, and the mixture was extracted three times with 200 mfl of ethyl ether, then washed with saturated brine, and then the solution was dried over anhydrous sodium sulfate. This solution was distilled under reduced pressure to remove ethyl ether.

A reddish brown oil was obtained.

Next, this oily substance was applied to the same silica gel column as in Example 1 and a developing solvent (hexane:ethyl acetate=2:).
6.1 g of red oil was obtained.

"HNMR spectrum (solvent: CDC) of the obtained compound
N., Reference material: Tetramethylsilane, equipment (JEOL
GX-270, manufactured by JEOL Ltd.): 270 MHz) and mass spectra (electron impact ionization method), this compound is 2-(2-methoxyvinyl)-5
-thiophenealdehyde (0)1cff)l-'CHO
C)1. , molecular weight 168). "H
The results of the NMR spectrum and mass spectrum are as follows.

18 NMR spectrum δ = 3.90 (311, s) 5.66 to 7.6 (4H, work) 9.83 (IH, s) Mass spectrum m/Z = 168 During separation and purification of the oily substance using a silica gel column The other fractions are 2-(2-methoxyvinyl)
-2-hydroxyvinyl-5-thiophenealdehyde (mass spectrum: m/Z = 154), which is a hydrolyzate of 5-thiophenaldehyde, and 2-formylmethyl-5-thiophenealdehyde (mass spectrum: m/Z = 154) Met.

Reference Example 1 4.9 g (31 mmoQ) of methyl 2.3.3-trimethylindoleninphonate was placed in a three-necked flask with a capacity of 200, heated to 130 to 140"C under a nitrogen atmosphere, and stirred for 5 hours. did.

Next, 2.5 g (1
5gnoIl) was added to the above reaction mixture, the temperature was raised to 150°C over about 5 minutes, and then allowed to cool to 100°C.

After cooling, 10 mQ of pyridine and 6 g of triethylamine were added to the reaction solution, and the mixture was stirred for 7 minutes. Next, 4.5g (3
After adding 50 mD of sodium iodide and 50 mD of ethanol and refluxing for 5 minutes, the mixture was allowed to cool.

The resulting reaction mixture was separated using the silica gel column and developing solvent (hexane: ethyl acetate = 2:1, volume ratio), and then separated using a reverse phase column (Roper column C-RP).
-18, Merck & Co., trade name) and a developing solvent (chloroform).

A black-rimmed solid cyanine dye of 450 wrg (isolated yield 2.4 go 12%) was obtained.

Reference Example 2 The reaction was carried out in the same manner as in Reference Example 1, except that ethyl P-toluenesulfonate was used instead of methyl P-toluenesulfonate, and sodium iodide was not used. The product was separated and purified in the same manner as in Reference Example 1 to obtain 630 mg of a black-rimmed solid cyanine dye.

Claims (1)

[Scope of Claims] (1) A thiophene derivative represented by the following general formula [I]. ▲There are mathematical formulas, chemical formulas, tables, etc.▼...[I] (In the formula, X is a hydrogen atom or -CHO group, Y is -CH=
CHOR group, -CH=CHOH group or -CH_2CH
Indicates an O group. Here, R represents an alkyl group having 1 to 8 carbon atoms. )(2)
The thiophene derivative according to claim 1, wherein X is a hydrogen atom and Y is a -CH=CHOCH_3 group. (3) X is -CHO group, Y is -CH=CHOCH
The thiophene derivative according to claim (1), which is a _3 group.