JPS62164664A - Production of 2-methyleneindoline compound - Google Patents

Abstract

PURPOSE:To readily obtain the titled compound useful as an intermediate raw material doer spiro compounds in good yield, by reacting a specific indolenine compound with a quaternizing agent and reacting the resultant indolenium salt without isolation with a basic substance. CONSTITUTION:An iodolenine compound expressed by formula I (R<1> and R<2> are 1-10C alkoxy; R<3> is 6-10C aryloxy, 7-11C aralkoxy, 1-6C alkoxy and alkyl, halogen, etc.; n is 0-4) is reacted with a quaternizing agent expressed by the formula R<4>-X [R<4> is 1-20C (substituted) alkyl, 3-10C (substituted) cycloalkyl, 7-20C (substituted) aralkyl, 6-14C aryl, etc.; X is anionic eliminative group] to give a reaction mixture, which is without isolation reacted with a basic substance, preferably triethylamine, NaOH, etc., to afford the aimed compound expressed by formula II. EFFECT:Novel spiro compounds, having good fatigue resistance and coloring and decoloring properties and rich in hues of coloring species can be synthesized.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention is applicable to printing, optical elements, recording materials, clothing, etc.
- A method for producing an intermediate material 11 of a spiro compound useful as a tochromic material 11 (for decorative items).

(Prior Art) 2-methyleneindoline compounds have been produced by reacting an indolenium salt (a quaternized product of an indolenine compound) with a base.

(Problems to be Solved by the Invention) Many indolenium salts are unstable and many are difficult to isolate. Therefore, NV is possible using the conventional method.
-The types of medilene indoline compounds were limited. There were problems such as low production yield.

(Means for Solving the Problems) The present invention relates to a %Aa method for 2-methyleneindoline compounds to solve the above problems. That is, the present invention allows the indolenine compound represented by the general formula (A) to react with the quaternizing agent R4-X, without isolating the resulting product, and subsequently adding a basic substance to the reaction mixture. A method for producing a 2-methyleneindoline compound represented by the general formula (B) tortoise.

(Here, R1 and R2 are alkyl having 1 to 10 carbon atoms, R
3 is an aryloxy group having 6 to 10 carbon atoms, and 7 to 1 carbon atoms;
1 aralkoxy group, alkoxy group having 1 to 6 carbon atoms, argyl group having 1 to 6 carbon atoms, halogen group, cyano group, acyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, carbon number It represents a substituent selected from an alkoxycarbonyl group having 2 to 10 carbon atoms, a halogen-substituted alkyl group having 1 or 2 carbon atoms, and a nitro group, and ") is an integer of 0 to 4, and R3 is the same or different. There may be.

R4 is an unsubstituted or substituted argyl group having 1 to 20 carbon atoms,
unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms,
aX representing a substituent selected from an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms and an unsubstituted or substituted aryl group having 6 to 14 carbon atoms is an anionic leaving group.

Some of the indolenine compounds used in the present invention are already commercially available, but for example, the indolenine compounds obtained by the cyclization reaction of a substituted phenylhydrazone of methyl-5ec-alkyl ketone?
! Created (by Masaki Ota, Heterocyclic Chemistry (Volume 1) R70,
Baifukan (1957)).

Representative examples of the quaternizing agent R4-X include alkyl (or aralkyl) halide compounds and sulfonate compounds. Some alkyl (or aralkyl) halide compounds R4-X are already on the market, for example, alkyl (or aralkyl> alcohol R4-X).
Produced by the reaction of -OH and dionyl halide 5OX2.

Examples of X include I, Br, (4,F), but from the viewpoint of reactivity, 1.Br and C0 are preferably used.

The sulfonate compound R4X is manufactured by the reaction of argyl (or aralkyl) alcohol and sulfonic acid chloride, for example, although some are commercially available as 1 (Qvgnic 5ynthesis, Co1Jec
tive VoLl, 145>. X here is represented by OS 02R, and specific examples of R include alkyl groups having 1 to 8 carbon atoms, halogen-substituted alkyl groups having 1 to 8 carbon atoms, halogen-substituted phenyl groups, carbon Numbers 1-8
(substituted with a nitro-substituted argyl group, a nitro-substituted phenyl group, and an alkyl group having 1 to 8 carbon atoms).

From the viewpoint of reactivity, halogen-substituted alkyl groups, para-substituted phenyl groups, and C1-C4 alkyl groups are preferably used. Zara has triful A [21 methyl base, 2.
2.2-trifluoroethyl, P-21-lophenyl group, P-methylphenyl group, P-bromophenyl group, and butyl group are preferably used.

R4 in the quaternizing agent is y with 1 to 20 carbon atoms! ((Substituted or directly substituted alkyl group, having 3 to 10 carbon atoms;!!!'
Represents a substituent selected from a substituted or substituted cycloalkyl group, an unsubstituted or substituted aralkyl group having 7 to 2 O carbon atoms, an unsubstituted or substituted aryl group having 6 to 14 carbon atoms, and is represented by the general formula (B). It is introduced into the 1-position of the 2-methylene indoline compound shown. Examples of R4 that can maximize the characteristics of the present invention include those with large steric hindrance such as isopropyl group, diphenylmethyl group, benzyl group and substituted benzyl group, naphdylmethyl group and substituted naphthylmethyl group.

The quaternization reaction is carried out without a solvent or in a solvent. As the solvent, any solvent other than a basic solvent can be used, but from the viewpoint of removing the solvent after the reaction and controlling the reaction temperature, organic solvents having a boiling point in the range of 30 to 160°C are preferably used. Ru.

For example, hydrocarbons such as benzene, toluene, xylene, and hexadi; sulfides such as carbon disulfide and dimethyl sulfoxide; chlorides such as methylene chloride and chloroform; polar abrothinic solvents such as acetone, methyl 1-derketone, acid-resistant ethyl, and acetonitrile II1. : Ether compounds such as tetrahydrofuran and dioxane; Polar protic solvents such as methanol, ethanol, methyl cellosolve, and dimethyl cellosolve. Although these may be used alone, they can also be used as a mixed solvent of two or more.

The conditions for the quaternization reaction are: trimethylindolenine compound,
Although it should be determined experimentally depending on the type of quaternizing agent and reaction solvent, the reaction time is 0.1 to 24
Regarding the time and reaction temperature, it is particularly preferable to carry out the reaction at a temperature near the reflux temperature of the solvent. The reaction between the trimethylindolenine compound and the quaternizing agent can be carried out by heating after mixing, but in order to prevent a decrease in the yield of the product due to oxidative decomposition, etc., each of them should be dissolved in a solvent and heated under inert gas before mixing. It is preferable to mix and heat after replacing with. Specific examples of the inert gas include nitrogen, helium, argon, and the like.

The quaternizing agent is 0 for the trimedelindolenine compound.
．． It is preferable to use 2 to 20 times the molar amount, especially 0
．． 5 to 3 times mole G1 is preferably used.

Note that if the temperature or time is lower than or shorter than the lower limit under the above conditions, each reaction will not proceed sufficiently, resulting in a decrease in the yield of the product.

Moreover, if it is higher than the upper limit or longer, the reaction product and/or the reaction raw material will disappear due to thermal decomposition etc., resulting in a decrease in the yield of the reaction product, which is not preferable. on the other hand,
Regarding the reaction molar ratio, if it deviates from the above range, the yield of the reaction product will decrease, which is not preferable.

Although some of the indolenium salts obtained from the quaternization reaction can be isolated, they are generally isolated. In the present invention, single 14It'1! tends to disappear due to oxidative decomposition during or after isolation. It is characterized by the transition to the next reaction without any reaction.

Next, the basic substance used in the production of the 2-methyleneindoline compound represented by the general formula (B) may be any organic or inorganic basic substance t1, but from the viewpoint of the reaction yield of the product, pyridine, triethylamine, etc. Amine compounds such as helium hydroxide and the like are preferably used.

The reaction product of an indolenine compound and a quaternizing agent and J3!
The conditions for producing a 2-methyleneindoline compound by reaction with an Ig substance include a reaction temperature of -130 to 160 °C.
Temperature conditions of .degree. C. are preferred, and 30 to 90.degree. C. is particularly preferably used. The basic substance is preferably used in an amount of 0.5 to 50 times the molar amount of the trimedelindolenine compound, particularly preferably 0.8 to 5 times the molar amount of the trimedelindolenine compound. Note that if the temperature is lower than the lower limit under the above conditions, the reaction will not proceed sufficiently and the yield of the product will decrease.

Moreover, if it is higher than the upper limit, the reaction product and/or the reaction raw material will disappear due to thermal decomposition etc., resulting in a decrease in the yield of the reaction product, which is not preferable. On the other hand, if the reaction molar ratio is out of the above range, the yield of the reaction product will decrease, which is not preferable.

The fraction of the 2-methyleneindoline compound thus obtained! For purification, column chromatographic separation methods using various supports and various developing solvents, solvent extraction methods, distillation methods, etc. can be used, and furthermore, a combination of these methods can also be carried out.

Specific examples of supports used in column separation methods include:
Examples include silica gel, alumino, cellulose, calcium hydroxide, and quicklime.

The developing solvent may be any solvent as long as it is compatible with the 2-methyleneindoline compound and is insoluble in the supporting carrier, and specifically, hydrocarbons such as benzene, toluene, and hexane, and chlorides such as chloroform and meburene chloride may be used. , atom, methyl ethyl carbon, ethyl acetate, etc. @A, t+
Abrotic solvents, needles such as detrahydrofuran and dioxane, polar protic solvents such as methanol and ethanol, and the like are used alone or as a mixed solvent.

The combination of various supporting carriers and various developing solvents should be determined experimentally depending on the solubility of the substance to be separated, the flow rate, etc.

In the solvent extraction method, a combination V of an organic solvent insoluble in water and soluble in the 2-methyleneidoline compound and water is preferably used. Specific examples of organic solvents that are insoluble in water include hydrocarbons such as bempine, toluene, and hegyonan; chlorides such as methylene chloride and di[10-form]; diethyl ether; and ethyl lactate.

The distillation method is usually preferably carried out under reduced pressure (0,001 to 0,1 mmf-1 g) for the purpose of preventing thermal decomposition and increasing the distillation rate.

The 2-methyleneindoline compound referred to as "AN" in the present invention is useful as an intermediate raw material for spiro compounds.

As spiro compounds, spirobenzobilane compounds represented by the general formula (C), spironaphthopyran compounds represented by the general formula, and spironaphthoxylidine compounds represented by the general formula (E) are known. [1Natsuto A Gisazine compound is a photochromic compound with good fatigue resistance and color development/decolorization (↑1), and is expected to find applications. 1-(16-substituted aralgyl)-spironaphtho-oxylidine produced by reaction of 1-(directly substituted aral=1-nyl)-2-methyleneindoline compound obtained by the method of the present invention and 1-nitroso-2-naphthol By introducing electron-withdrawing 11 as a substituent, the compound can shorten the wavelength of the absorption of the coloring species.
Conversely, by introducing an electron-withdrawing f1 group, the absorption of the coloring species can be made to have a longer wavelength.

Rinawara 1 with this invention! The 2-methyleneindoline compound treated as iI has a white color [4
An intermediate material for 1-(substituted aralgyl)-spironaphth oxylidine compounds which has good color properties and a rich variety of hues.
It is useful as

Example 1 ■ Synthesis of 1-benzyl-3,3-dimethyl-2-medyleneindoline 2.3.3-Trimedellindolenine 20Q was dissolved in 50d of toluene, and benzyl bromide 20q was dissolved in 50d.
The mixture was dissolved in toluene, blown with nitrogen gas for 10 minutes, mixed, and refluxed in a nitrogen stream for 2 hours. After that, the temperature of the reaction solution was lowered to 30'C, and 1 to riedylamine 2
Add 0q and stir for 30 minutes. After the reaction, the mixture is condensed and subjected to column chromatography using alumina as a support and toluene as a developing solvent. After distilling off the toluene, 1q of red Ayl was distilled under reduced pressure to convert 20Q of 1-benzyl-3,3-dimethyl-2-mebuleneindoline into 1-no.

1660cm-1 (C=C) ■ Application example 1-Benzyl-3,3-thumeblue 2-methyleneindoline and equimolar amount of 1-nitroso-2-naphthol were dissolved in ethanol and refluxed for 1 hour to form 1- Benzyl-3,3-dimethylspiro[indoline-2,3--
[]-]1]-Nut2.1-b] (1,4) oxylydine] is 1q.

(Elemental analysis value) Actual value (%) h1 calculated value (%) C83,
383,2 1-15,85,9 N 6.8 6.91-Benzyl-
3,3-dimethyl-2-methyleneindoline and equimolar amount of 2-hydroxy-1-soft aldehyde were dissolved in butanol and centrifuged for 15 minutes to form 1-benzyl-3,3-dimethylspiro[indoline]. -2,3”
-[3)-1] -nando[2,1-b]pyran] to 1
! 7.

(Elemental analysis value> Actual value (%) Kl calculation (%) C
86,686,4)1 6.2 6.2N
3.4 3. b Example 2 ■ Synthesis of 1-(2,3,4,5,6-pentaflu A[1benzyl)-3,3-dimethyl-2-methyleneindoline 2.3.3-trimethylindolenine 20C] 50t
Dissolve in nll property tool, 2.3.4,5゜6-
Pentafluorobenzyl tosylate 30C] is 507!
After blowing nitrogen gas into each solution for 10 minutes, the mixture was mixed and refluxed for 2 hours in a nitrogen stream. Thereafter, the temperature of the reaction solution was lowered to 60'C, 20% aqueous sodium hydroxide solution 30Q was added, and the mixture was stirred for 30 minutes. After the reaction,
After distilling off the propatool, add chloroform and cover with solvent extraction. The chromoform layer was concentrated, and the red oil obtained was distilled under reduced pressure to obtain 20Q of 1-(2,3,
4,5゜6-pentafluorobenzyl)-3,3-dimethyl-2-methyleneindoline'+! ? Ta.

■ Application example 1 - (2,3,4,5,6-pentafluorobenzyl)-3,3-dimethyl-2-methyleneindoline and equimolar amounts of 1-nide [1-so-2-naphthol are dissolved in toluene. and reflux for 1 hour, 1-(2,3,4,
5,6-pentafluorobenzyl)-3,3-dimethylspiro[indoline-2,3-[3H]-nando[2
, 1-b] (1゜4) OKIJIN] was) q.

(Elemental analysis value) Actual value (%> it calculated value (%) C
68,067,5 N 3.8
3.8N 5.6 5.6
1-(2,3,4,5,6-pentafluorobenzyl)-3,3-dimethyl-2-methyleneindoline and equimolar amount of 5-nitrolilydyl aldehyde were dissolved in arene and incubated for 1 hour. By flowing, 1-1 (2, 3, 4
.

(Elemental analysis value) Actual value (%>hl sieve (%) C75,
375,4 1+ 5. 4
5. 5N 7.0
7.0 (Effects of the invention) ■ It became possible to produce a 2-methyleneindoline compound that could not be obtained by conventional methods. In 1z1, it has become possible to perform rXM of 2-methyleneindoline compounds in which sterically bulky groups such as isopropyl, benzyl groups, substituted benzyl groups, naphdylmethyl groups, and substituted benzyl groups are placed in the 1st position.

(2) Using the 2-methyleneindoline compound produced by the present invention as an intermediate raw material, it has become possible to synthesize a novel Spi[1 compound.

Claims (1)

[Claims] General formula (A) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(A) An indolenine compound and a quaternizing agent R^4-X
General formula (B) characterized in that the reaction mixture is subsequently reacted with a basic substance without isolating the product obtained by reacting with ) A method for producing a 2-methyleneindoline compound represented by: (Here, R^1 and R^2 are an alkyl group having 1 to 10 carbon atoms, R^3 is an aryloxy group having 6 to 10 carbon atoms, an aralkoxy group having 7 to 11 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. group, alkyl group having 1 to 6 carbon atoms, halogen group, cyano group, acyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, 1 to 10 carbon atoms, or 2 halogen-substituted alkyl group,
It represents a substituent selected from nitro groups, n is an integer of 0 to 4, and R^3 may be the same or different. R^4 is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an unsubstituted or substituted cycloalkyl group having 3 to 10 carbon atoms, an unsubstituted or substituted aralkyl group having 7 to 20 carbon atoms, or an unsubstituted or substituted aralkyl group having 6 to 14 carbon atoms. It represents a substituent selected from unsubstituted or substituted aryl groups, and X represents an anionic leaving group. )