JP2980442B2 - Dihydroxyetheramine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel dihydroxyetheramine and an acid addition salt thereof which can be used as raw materials for synthetic detergents, pharmaceutical intermediates, agricultural chemical intermediates, chemicals for rubber, surfactants, raw materials for producing organic products, and the like. It is intended to provide a novel Schiff base which is a raw material for producing the dihydroxyetheramine.

[0002]

2. Description of the Related Art Journal of Organic Chemistry (J. Org. Chem.), Vol. 8, p. 189,
In 1943, 1-amino-3-
(2-Hydroxyethoxy) -2-propanol has been described.

[0003]

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[0004]

However, the use of the above compounds is not specifically described.

The present inventors have tried to add the above compound to a developing solution for the purpose of improving the wettability with the photoresist by adding it to the existing solution of the photoresist and improving the development. . As a result, the photoresist was left undeveloped, a sharp developed pattern was not obtained, and a good developing solution could not be obtained.

[0006]

The inventors of the present invention have conducted a series of studies on hydroxyamines for the purpose of obtaining a good photoresist solution, and have found that novel dihydroxyetheramines containing ether groups and The inventors have found an acid addition salt thereof and a novel Schiff base which is an intermediate for producing the dihydroxyetheramine, thereby completing the present invention.

That is, the present invention provides a compound represented by the general formula

[0008]

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Wherein R 1, R 2, and R 3 represent hydrogen and an alkyl group, and n represents 0 or an integer of 2 to 20;
General formula

[0010]

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(Wherein, R 1, R 2 and R 3 represent hydrogen and an alkyl group, n represents 0 or an integer of 2 to 20, and AH represents an acid) Acid addition salts, and the general formula

[0012]

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(Wherein, Ar represents an aryl group which may be substituted, R ¹ , R ² and R ³ represent hydrogen and an alkyl group, and n represents an integer of 0 to 20). The Schiff base shown.

In the general formula (I), the alkyl group represented by R ¹ , R ² and R ³ is not particularly limited.
A linear or branched one is used. The number of carbon atoms is not particularly limited, but those having 1 to 4 carbon atoms are preferable from the viewpoint of easy availability of raw materials. Examples of suitable alkyl groups in the present invention include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, and an iso-
Examples thereof include a butyl group, a sec-butyl group and a t-butyl group.

The value of n is not particularly limited as long as it is in the range of 0 to 20, but is preferably 0 to 4 from the viewpoint of easy availability of raw materials.

Specific examples of the compound of the present invention represented by the above general formula (I) include 1-amino-2- (2,3-
Dihydroxypropoxy) ethane, 1-amino-3-
(2,3-dihydroxypropoxy) propane, 1-amino-4- (2,3-dihydroxypropoxy) butane, 1-amino-5- (2,3-dihydroxypropoxy) pentane, 1-amino-6- (2 , 3-Dihydroxypropoxy) hexane, 2-amino-1- (2,3-
Dihydroxypropoxy) propane, 2-amino-1-
(2,3-dihydroxypropoxy) butane, 2-amino-1- (2,3-dihydroxypropoxy) pentane, 2-amino-1- (2,3-dihydroxypropoxy) hexane, 2-amino-1- (2 , 3-Dihydroxypropoxy) -3-methylbutane, 2-amino-4-
(2,3-dihydroxypropoxy) pentane, 2-amino-4,5-dimethyl-4- (2,3-dihydroxypropoxy) heptane, 6-amino-2,2,3-trimethyl-3- (2,3 -Dihydroxypropoxy) octane, 7-amino-2,2,3-trimethyl-3-
(2,3-dihydroxypropoxy) nonane and the like can be mentioned.

In the formula (II), the alkyl group represented by R ¹ , R ² and R ³ and n can be the same as those described in the formula (I). The acid represented by AH is not particularly limited, and an inorganic acid or an organic acid is used. For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid or acetic acid, benzoic acid, phthalic acid, fumaric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, p-toluenesulfonic acid, methanesulfonic acid And the like.

Specific examples of the compounds of the present invention represented by the general formula (II) are as follows: hydrochloride, sulfate, nitrate, phosphate, Acetate, benzoate, phthalate, fumarate, laurate, myristate, palmitate, stearate, oleate, p-toluenesulfonate, methanesulfonate, etc. .

In the general formula (III), the aryl group represented by Ar is a phenyl group, a naphthyl group or the like.
This aryl group may be substituted or unsubstituted. As the substituent, a halogen atom, an alkyl group,
Examples thereof include an alkoxyl group, an alkylthio group, a nitro group, and a cyano group. However, it is preferably unsubstituted in view of availability of raw materials.

In the general formula (III), R ¹ , R ² ,
And the alkyl group represented by R ³ and n can be the same as those described in the above formula (I). Specific examples of the compound of the present invention represented by the general formula (III) include N- (phenylmethylene) -2- (2,3-epoxypropoxy) -1-ethylamine, N- (phenylmethylene) -3- (2,3-epoxypropoxy)-
1-propylamine, N- (phenylmethylene) -4-
(2,3-epoxypropoxy) -1-butylamine,
N- (phenylmethylene) -5- (2,3-epoxypropoxy) -1-pentylamine, N- (phenylmethylene) -6- (2,3-epoxypropoxy) hexylamine, N- (phenylmethylene)- 1- (2,3-epoxypropoxy) -2-propylamine, N- (phenylmethylene) -1- (2,3-epoxypropoxy)
-2-butylamine, N- (phenylmethylene)-
(2,3-epoxypropoxy) -2-pentylamine, N- (phenylmethylene) -1- (2,3-epoxypropoxy) -2-hexylamine, N- (phenylmethylene) -1- (2,3 -Epoxypropoxy) -3
-Methyl-2-butylamine, N- (phenylmethylene) -4- (2,3-epoxypropoxy) pentylamine, N- (phenylmethylene) -4,5-dimethyl-
5- (2,3-epoxypropoxy) -2-heptylamine, N- (phenylmethylene) -2,2,3-trimethyl-3- (2,3-epoxypropoxy) -6-octylamine, N- ( Phenylmethylene) -2,2,3-
Trimethyl-3- (2,3-epoxypropoxy) nonylamine and the like can be mentioned.

The general formulas (I), (II) and
The structure of the compound represented by the general formula (III) can be confirmed by the following means.

(1) ¹ H-nuclear magnetic resonance spectrum ( ¹ H-N
By measuring MR), the above general formulas (I) and (I)
The bonding mode of hydrogen atoms present in the compounds represented by I) and (III) can be known.

(2) By measuring the infrared absorption spectrum (IR), the above-mentioned general formulas (I), (II) and (II)
The characteristic absorption derived from the functional group of the compound represented by I) can be observed. Formula absorption based on O-H bonds and N-H bonds in the vicinity of 3600～2500Cm ^-1 is a compound represented by the formula (I), in the vicinity of 1150 cm ^-1 C-
Characteristic absorption based on the OC bond can be observed.
In the compound represented by the general formula (II), 3200 cm
^-1 near absorption due to NH ₃ ⁺ NH bond, 1150c
Characteristic absorption based on C—O—C bonds can be observed around m ⁻¹ . When A-H is an organic carboxylic acid, the absorption based on the C ＝ O bond of the carboxylate is observed around 1680 cm ⁻¹ , and when sulfuric acid is S400 around 1400 cm ^−1.
Absorption due to O-bonds can be observed.

In the compound represented by the general formula (III),
3600～2800Cm ^-1 vicinity based on O-H bond absorption, absorption based on C-O-C absorption at around 1150 cm ^-1, absorption based on the aromatic C = C bond in the vicinity of 1650 cm ^-1, around 1550 cm ^-1 Absorption based on C = N bond, 1
Characteristic absorption based on epoxy groups can be observed at around 250 cm ^-1 .

(3) A mass spectrum (MS) is measured, and a composition formula corresponding to each observed peak (generally, a value represented by m / e obtained by dividing the mass number m of the ion by the charge number e of the ion). By calculating, the bonding mode of each atomic group in the molecule of the compound subjected to the measurement can be known. That is, the dihydroxyetheramine represented by the general formula (I) generally has a molecular ion peak (hereinafter, referred to as a molecular ion peak).
M ⁺ From abbreviated) and 1 (peak of M ⁺ -1 obtained by subtracting the corresponding proton), M ⁺ a 18 (H ₂ corresponding to O) the subtracted M ⁺ -18 peak and CH ₂ (O
H) A characteristic peak corresponding to CH ⁺ is observed.

The Schiff base compound represented by the general formula (III) has a peak corresponding to M ⁺ -1;
A peak corresponding to CH ₂ (O) CHCH ₂ ⁺ , C ₆ H ₅ CH
A characteristic peak corresponding to = NCH ₂ ⁺ is observed.

(4) Carbon, hydrogen, nitrogen,
By subtracting the sum of the weight percentages of chlorine and sulfur and each element from 100, the weight percentage of oxygen can be calculated, and thus the composition formula can be determined.

Further, dihydroxy ether amine represented by the general formula (I), R ¹ in the general formula (I),
The properties are slightly different depending on the type of R ² and R ³ and the value of n, but it is a colorless or pale yellow viscous liquid having a boiling point. Specifically, as shown in the synthesis examples described later, as in the case of general organic compounds, the above compounds tend to have a higher boiling point as the molecular weight increases. The compound is soluble in highly polar organic solvents such as alcohols such as methanol and ethanol, N, N-dimethylformamide, dimethylsulfoxide, and chloroform, and in water, but is soluble in less polar solvents such as carbon tetrachloride and hexane. Is almost insoluble.

The acid addition salts of dihydroxyetheramine represented by the general formula (II) include the types of R ¹ , R ² and R ³ , the value of n and the type of AH in the general formula (II). It is a colorless or pale yellow viscous liquid or solid, although its properties vary slightly depending on the type. The compound is soluble in water, alcohols such as methanol and ethanol, and solvents such as N, N-dimethylformamide and dimethylsulfoxide.

The Schiff base represented by the general formula (III) is a compound represented by Ar, R ¹ , R ² and R ^{3 in the} general formula (III).
Is a colorless or pale yellow viscous liquid or solid, and has a boiling point. Specifically, as shown in the synthesis examples described below, the boiling point of the compound tends to increase as the molecular weight increases, as in a general organic solvent. The compound is methanol,
It is soluble in organic solvents such as alcohols such as ethanol, halogenated hydrocarbons such as methylene chloride and chloroform, and aromatic hydrocarbons such as benzene and toluene, but is insoluble in water.

The dihydroxyetheramine represented by the general formula (I), the acid addition salt of the dihydroxyetheramine represented by the general formula (II) and the dihydroxyetheramine represented by the general formula (II)
The following method can be mentioned as a typical method for producing the Schiff base represented by I). That is, a Schiff base of an amino alcohol (a compound represented by the following general formula (IV)) is used as an alcoholate (a compound represented by the following general formula (V)), and epihalohydrin (a compound represented by the following general formula (VI))
To produce the compound represented by the general formula (III), and then hydrolyzed in the presence of an acid catalyst, and neutralized with an alkali to obtain the compound represented by the general formula (I) And then neutralized with an acid to obtain the compound represented by the general formula (II).

[0032]

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(Wherein X represents a chlorine atom, bromine atom or iodine atom, M represents an alkali metal, R ¹ , R ² , R ³
And n are the same as in the general formulas (I), (II) and (III), and AH is the same as in the general formula (II). ) A reaction between a Schiff base of an amino alcoholate [compound represented by the general formula (V)] and epihalohydrin [a compound represented by the general formula (VI)] (hereinafter abbreviated as reaction (1)) In)), the Schiff base of amino alcoholate as a raw material can be produced by a known method. That is, it can be easily obtained by reacting a corresponding amino alcohol with a corresponding aryl aldehyde in an organic solvent and then reacting with an alkali metal hydride or an alkali metal alkyl. Examples of the alkali metal hydride include lithium hydride, sodium hydride, and potassium hydride. The alkali metal alkyl is not particularly limited, but preferred examples thereof include n-butyllithium and t-butyllithium.
-Butyl lithium and the like. The charge molar ratio of the Schiff base of the amino alcohol and the alkali metal hydride or the alkali metal alkyl may be appropriately determined as necessary, but it is usually the case that an equimolar amount or a slightly excessive amount of the alkali metal hydride or the alkali metal alkyl is used. General.

In the reaction (1), as the alkali metal represented by M, sodium, potassium, lithium and the like are usually used.

In the reaction (1), the charged molar ratio of aminoalcoholate to epihalohydrin may be appropriately determined as necessary, but it is usual to use epihalohydrin in a slightly excessive amount.

In the reaction (1), it is generally preferable to use an organic solvent. Examples of the solvent preferably used include aliphatic or aromatic hydrocarbons such as benzene, toluene, xylene and heptane; ethers such as diethyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether; acetonitrile and the like. Nitriles; N, N-dimethylformamide;
N, N-dialkylamides such as N, N-dimethylacetamide and the like.

The reaction temperature is generally -5.
It is sufficient to select from the range of 0 to 150 ° C, preferably -20 to 40 ° C. The reaction time varies depending on the type of the raw material, but it is usually sufficient to select from a range of 1 hour to 3 days, preferably 4 to 40 hours. During the reaction,
Preferably, stirring is performed.

The method for isolating and purifying the compound of the general formula (III) obtained by the above reaction (1) is not particularly limited. For example, after distilling off the reaction solvent, the residue is subjected to chloroform, benzene, ether or the like. Extract with organic solvent. After washing with water, the organic layer is dried with a desiccant such as anhydrous sodium sulfate or calcium chloride, then the organic solvent is distilled off, and the residue is subjected to vacuum distillation to obtain the desired product.

In the method shown above, in the reaction for converting the compound represented by the general formula (III) into the compound represented by the general formula (II) (hereinafter abbreviated as reaction (2)), The acid aqueous solution used is not particularly limited, and an aqueous solution of an inorganic acid or an organic acid is used. Particularly preferred examples of the inorganic acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, and the like. Particularly preferred examples of the organic acid include acetic acid, p-toluenesulfonic acid, methanesulfonic acid, and the like. is there. The concentration of the aqueous acid solution is generally 0.1 to 4
It is sufficient to select from the range of 0%, preferably 5 to 20%. The reaction temperature is generally 5 to 100.
C., preferably within the range of 10 to 40.degree. The reaction time is usually 1 hour to 3 days, preferably 10 to
It is enough to choose from a range of 40 hours. During the reaction, it is preferable to carry out stirring. The general formula (III)
The amount of the compound represented by is generally 1 to 300 g / L, preferably 10 to 30 g, in an aqueous acid solution.
/ L.

The reaction solution obtained by hydrolysis with an aqueous acid solution is extracted with an organic solvent such as benzene, chloroform or ether to remove the generated aryl aldehyde.
The aqueous layer is neutralized with alkali. The alkali is not particularly limited, but an alkali metal hydroxide and an alkali metal carbonate are preferably used. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide, and examples of the alkali metal carbonate include sodium carbonate,
Examples thereof include sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, lithium carbonate, lithium hydrogen carbonate and the like. The method of adding these is not particularly limited, but they may be added as an aqueous solution or may be added as they are. The amount of alkali added is preferably equimolar to the acid used for hydrolysis.

The method for isolating and purifying the compound represented by the general formula (I) obtained in the above reaction (2) is not particularly limited.
For example, after distilling off water after neutralization, the residue is ethanol, i
So-propanol, alcohol such as n-butanol or chloroform, extracted with an organic solvent such as a halogenated hydrocarbon such as methylene chloride and the like to remove insoluble components, after distilling off the organic solvent, by vacuum distillation of the residue, The desired product can be obtained.

The reaction for converting the compound represented by the general formula (I) into the compound represented by the general formula (II),
The method for forming an acid addition salt of the compound represented by the general formula (I) (hereinafter, abbreviated as reaction (3)) is not particularly limited, and it can be easily produced according to a conventional method. For example, an aqueous solution of an acid may be added to the compound represented by the general formula (I), and water may be distilled off. Here, as the acid, any of AH described above can be used without any limitation. The acid addition amount is equimolar to the compound of the above formula (I) if AH is a monobasic acid, １ ／ mole when AH is a dibasic acid, and AH is a tribasic acid. 1/3 for acid
It may be twice the mole. The general formula (II) obtained in the above reaction (3)
The method for isolating the compound represented by I) is not particularly limited, and for example, water used as a solvent may be distilled off.

[0043]

The compound represented by the general formula (I) of the present invention can be used as a raw material for synthetic detergents, a pharmaceutical intermediate, an agricultural chemical intermediate, a chemical for rubber, a surfactant, and an organic intermediate raw material. In particular, the compound represented by the above general formula (I) of the present invention can be used as a surfactant such as an organic base soap or a fatty acid alkylolamide. For example, it can be used in a positive photoresist developing solution used in the field of microelectronics. By adding the compound, the wettability of the developing solution to the photoresist can be improved, and a good pattern can be formed with high resolution.

Among the compounds represented by the above general formula (II) of the present invention, salts of organic acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid are useful as organic base soaps. .

The compound represented by the general formula (III) of the present invention is a raw material for producing the compounds represented by the general formulas (I) and (II).

[0046]

EXAMPLES In order to explain the present invention more specifically, the following will be described.
The present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1- (a) In a 100 ml four-necked flask, 50 ml of tetrahydrofuran (hereinafter abbreviated as THF) and 14.9 g of N- (phenylmethylene) -2-hydroxyethylamine were dissolved and cooled to 10 ° C. 60% sodium hydride4.
4 g were added. After the generation of hydrogen stopped, 27.8 g of epichlorohydrin was added, and the mixture was stirred at 20 ° C for 20 hours. After distilling off THF under reduced pressure, ethyl ether 10
0 ml was added, and the mixture was washed twice with 100 ml of water. After drying over anhydrous sodium sulfate, the ethyl ether was distilled off, and the residue was distilled under reduced pressure (bp = 138 ° C./0.1 mmHg) to obtain 13.3 g of a pale yellow viscous liquid (yield = 65%).

As a result of measuring the infrared absorption spectrum of this product, an absorption based on an epoxy group was found at 1250 cm ⁻¹ ,
Absorption based on ether group at 20 cm ^-1 , 3600-25
Hydroxyl ^- based absorption at 00 cm ^-1 and C at 1150 cm ^-1
= Absorption based on N, absorption based on phenyl group at 1650 cm ^-1 . Its elemental analysis value was C 70.18%, H
7.41%, N 6.88% and the composition formula C ₁₂ H ₁₅
C 7, a calculated value for NO ₂ (205.28)
The results agreed well with 0.21%, H 7.38% and N 6.82%.

Further, as a result of measuring a mass spectrum, m
/ E204 peak corresponding to M ⁺ -1 in, m / e57 in CH ₂ (O) CHCH ₂ ⁺ to the corresponding peak, m / e11
FIG. 8 shows a peak corresponding to C ₆ H ₅ CH ＝ NCH ₂ ⁺ .

Further, ¹ H-nuclear magnetic resonance spectrum (δ:
ppm: tetramethylsilane standard; heavy chloroform solvent) was measured, and the results were as follows.

[0051]

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A multiple line corresponding to 9 protons was shown at 2.6 to 4.0 ppm, which corresponded to the methylene protons and methine protons of (a), (b), (c), (d) and (e). 1
A singlet line for one proton is shown at 0.5 ppm, and (f)
Methine proton. A multiline corresponding to 5 protons was shown at 7.2 to 7.8 ppm, which corresponded to the proton on the benzene ring in (g).

From the above results, the isolated product was N- (phenylmethylene) -2- (2,3-epoxypropoxy).
It was found to be -1-ethylamine.

Example 1- (b) In a 2000 ml flask, 1000 g of 10% sulfuric acid and N- (phenylmethylene) -2 obtained in Example 1- (a) were added.
20.50 g of-(2,3-epoxypropoxy) -1-ethylamine were added at room temperature. After stirring at 20 ° C. for 18 hours, the mixture was extracted twice with ethyl ether. 816 g of 10% sodium hydroxide was added to the aqueous layer. After water was distilled off under reduced pressure, 300 ml of ethanol was added, and the ethanol obtained by filtering off insolubles was distilled off to obtain 27.0 g of a yellow viscous oil. Distillation under reduced pressure (bp = 181 ° C .; 0.1 mmHg) gave 5.94 g of a pale yellow viscous oil (yield = 4).
4%).

[0055] As a result of measuring the infrared absorption spectrum of the absorption based on amino group and a hydroxyl group in the vicinity of 3600~2800cm ^-1, O-C-O in the vicinity of 1,120 cm ^-1
An absorption based on binding was obtained. The chart of the infrared absorption spectrum is shown in FIG.

Elemental analysis: C: 44.48%; H: 9.
75%, N 10.28% and C ₅ H ₁₃ NO ₃ (13
5.19). C 44.42%,
H was 9.71% and N was 10.36%.

Further, as a result of measuring a mass spectrum, m
/ E = 134, peak corresponding to M ⁺ −1, m / e ==
117, peak corresponding to M ⁺ -18 (H ₂ O), m / e
= 44, a peak corresponding to CH ₂ (OH) CH ⁺ was shown.

Further, ¹ H-nuclear magnetic resonance spectrum (δ:
ppm: based on tetramethylsilane; based on heavy chloroform), the results were as follows.

[0059]

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A triplet of two protons was shown at 2.8 ppm, which corresponded to the methylene proton of (h). 3.2-
A broad multiplet of 9 protons was shown at 4.0 ppm, which corresponded to the methylene and methine protons of (i) (j) (k) (l). The chart of the ¹ H-nuclear magnetic resonance spectrum is shown in FIG.

From the above results, it was found that the isolated product was 1-amino-
It was found to be 2- (2,3-dihydroxypropoxy) ethane. Example 1- (c) 1-amino-2- (2,3) obtained in Example 1- (b)
100 ml of 1N hydrochloric acid was added to 13.52 g of -dihydroxypropoxy) ethane, and water was distilled off to obtain 17.0 g of a pale yellow viscous oil.

As a result of measuring the infrared absorption spectrum of this product, an absorption based on the NH bond of NH ₃ ⁺ was obtained at around 3200 cm ⁻¹ .

The elemental analysis was as follows: C 35.05%, H 9.
35%, N 8.10%, Cl 20.59%, which are calculated values for the composition formula C ₅ H ₁₆ NO ₃ Cl (171.66), C 34.98%, H 9.41%, N
This was in good agreement with 8.16% and Cl 20.66%.

From the above results, the isolated product was found to be 2- (2,3
-Dihydroxypropoxy) ethyl-1-amine hydrochloride.

Example 2- (a) The same operation as in Example 1- (a) was carried out except that 16.3 g of N- (phenylmethylene) -3-hydroxy-1-propylamine was used as a raw material. Finally, the product was purified by distillation under reduced pressure (bp = 184 ° C./0.1 mmHg).
10.5 g of-(phenylmethylene) -2- (2,3-epoxypropoxy) -1-propylamine was obtained. The yield was 48%.

The measurement results of infrared absorption spectrum, elemental analysis, mass spectrum, and ¹ H-nuclear magnetic resonance spectrum are shown below.

Infrared absorption spectrum 3600-2500
absorbing element based on the absorption 1650cm ^-1 C-C (aromatic) based on cm ^-1 absorption 1130cm based on absorption 1250 cm ^-1 epoxy groups based on the OH bond ^-1 C-O-C in based absorption 1550 cm ^-1 C = N Analysis C ₁₃ H ₁₇ NO ₂ = 219.31 Found C 71.05%, H 7.88%, N 6.3
0% Calculated C 71.19%, H 7.83%, N 6.3
9% mass spectrum m / e 218 M ⁺ -1 m / e 118 C ₆ H ₅ -CH = N-CH ₂ ⁺ m / e 57 CH ₂ (O) CHCH ₂ ^{+ 1} H-nuclear magnetic resonance spectrum (δ: ppm: tetramethylsilane standard, heavy chloroform solvent)

[0068]

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(A) (b) (c) (d) (e) (f) Multiplex
11 protons δ: 2.6 to 3.9 ppm (g) Singlet proton 1 δ: 10.5 ppm (h) Multiplet proton 5 δ: 7.2 to 7.9 ppm Example 2- (b) N- as raw material (Phenylmethylene) -2- (2,3-
The same operation as in Example 1- (b) was carried out except that 21.9 g of (epoxypropoxy) -1-ethylamine was used.
1-amino-3, a pale yellow oil of 0.05 mmHg
-(2,3-dihydroxypropoxy) -propane7.
75 g were obtained. The yield was 52%.

The measurement results of the infrared absorption spectrum, elemental analysis, mass spectrum, and ¹ H-nuclear magnetic resonance spectrum are shown below.

Infrared absorption spectrum 3600-2800 cm ^-1 Absorption based on OH bond and NH bond 1130 cm ^-1 Absorption based on C--O-C Elemental analysis C ₆ H ₁₅ NO ₃ = 149.22 Actual value C 48.20% , H 10.05%, N 9.
44% Calculated C 48.29%, H 10.15%, N 9.
39% mass spectrum m / e 148 M ⁺ -1 m / e 130 M ⁺ -18 (H ₂ O) m / e 44 CH ₂ (OH) CH ^{+ 1} H-nuclear magnetic resonance spectrum (δ: ppm: tetramethyl Silane standard, heavy chloroform solvent)

[0072]

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(A) Triplet for two protons δ: 2.8 ppm (b) (c) (d) (e) (f) Multiline for 11 protons δ: 3.1 to 3.9 ppm Example 2- (c) 14.9 g of 1-amino-3- (2,3-dihydroxypropoxy) -propane and 1N sulfuric acid 1
The same operation as in Example 1- (c) was performed except that 00 ml was used, and finally water was distilled off to obtain a pale yellow solid 24.7.
g was obtained.

The measurement results of infrared absorption spectrum and elemental analysis are shown below.

Infrared absorption spectrum 3200 cm ^-1
Absorption based on NH bond of NH ₃ ⁺ 1130 cm ^-1 Absorption based on C—O—C bond 1400 cm ⁻¹ Absorption based on S ＝ O bond of sulfate Elemental analysis C ₆ H ₁₇ NO ₇ S = 247.30 Observed value C 28.91%, H 6.89%, N 5.6
1, S 12.90% Calculated C 29.14%, H 6.94%, N 5.6
7, S 12.96% Examples 3- (a) to 33- (a) In Example 1- (a), the Schiff bases described in Table 1 were synthesized by changing the raw materials used. The synthesized compound was a colorless or pale yellow viscous oil. Table 1 also shows the structure, yield, elemental analysis value, and infrared absorption spectrum of the obtained compound.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

[Table 7]

[0083]

[Table 8]

Examples 3- (b) to 32- (b) Dihydroxyetheramines shown in Table 2 were synthesized in the same manner as in Example 1- (b), except that the raw materials used were changed. The synthesized compound was a colorless or pale yellow viscous oil. Table 2 also shows the structure, yield, elemental analysis value, and infrared absorption spectrum of the obtained compound.

[0085]

[Table 9]

[0086]

[Table 10]

[0087]

[Table 11]

[0088]

[Table 12]

[0089]

[Table 13]

[0090]

[Table 14]

[0091]

[Table 15]

[0092]

[Table 16]

Examples 3- (c) to 36- (c) The acid addition salts of dihydroxyetheramine shown in Table 3 were synthesized in the same manner as in Example 1- (c), except that the raw materials used were changed. The synthesized compound was a colorless or pale yellow viscous oil or solid. Table 3 also shows the structure, elemental analysis values, and infrared absorption spectrum of the obtained compound.

[0094]

[Table 17]

[0095]

[Table 18]

[0096]

[Table 19]

[0097]

[Table 20]

[0098]

[Table 21]

[0099]

[Table 22]

[0100]

[Table 23]

[0101]

[Table 24]

[0102]

[Table 25]

Application Example 1 A 0.25% by weight aqueous solution of each of the compounds obtained in Examples 1- (c) to 36- (c) was prepared.
A 0.25% by weight aqueous solution of amino-3- (2-hydroxyethoxy) -2-propanol laurate was prepared. 40 ° C to evaluate the ability as a surfactant
The surface tension of each aqueous solution was measured and calculated by du Nouy's smooth method. Table 4 shows the measurement results.

The compound numbers correspond to the examples in which the compounds were synthesized.

[0105]

[Table 26]

Application Example 2 2.4% by weight of tetramethylammonium hydroxide
A photoresist developer was prepared by mixing the compounds of the present invention synthesized in Examples 1- (b) to 32- (b) with the aqueous solution in an amount shown in Table 5.

Next, a positive photoresist containing a novolak resin and a naphthoquinonediazide compound as main components was applied to a silicon wafer to a thickness of 1.3 μm, and then prebaked in a clean oven at 90 ° C. for 30 minutes. After a pattern was printed on this silicon wafer with a stepper (NSR1505G, manufactured by Nikon Corporation), development was carried out by immersion for 1 minute at a liquid temperature of 22 ° C. using the prepared developer. The photoresist pattern thus obtained was observed with a scanning electron microscope, and the pattern shape, the presence or absence of undeveloped portions, and the state of the bottom of the pattern base were evaluated.

Table 5 shows the results. In Table 5, the shape of the pattern means that the base of the pattern in the observation of the pattern was well cut and the shape was good.
On the other hand, when the base of the pattern was skirted or the shape was defective, the result was indicated by x.

For comparison, when a 2.4% by weight aqueous solution of tetramethylammonium hydroxide alone was used as a developing solution, and when a 2.4% by weight aqueous solution of tetramethylammonium hydroxide was mixed with a known 1-amino-3-
Table 5 shows (2-hydroxyethoxy) -2-propanol.
Table 5 also shows the cases where the amounts shown in Table 2 were used as a developer.

In Table 5, the compound numbers correspond to the numbers of the examples in which the compounds were synthesized, and the comparative compound was 1
-Amino-3- (2-hydroxyethoxy) -2-propanol.

[0111]

[Table 27]

[0112]

[Table 28]

[0113]

[Table 29]

[Brief description of the drawings]

FIG. 1 is a chart of an infrared absorption spectrum of the compound of the present invention obtained in Example 1- (b).

FIG. 2 is a chart of the ¹ H-nuclear magnetic resonance spectrum of the compound of the present invention obtained in Example 1- (b).

Claims (3)

(57) [Claims] R1 R3 OH OH (wherein R1, R2 and R3 represent a hydrogen or an alkyl group; and R2 | NH2CH (CH2) nCOCH2CH-CH2 (I) ||| R1R3OHOH And n represents 0 or an integer of 2 to 20). 2. A compound of the general formula: ## STR2 ## R2 │A--H.NH2 CH (CH2) nCOCH2 CH--CH2 (II) ││││R1 R3 OH OH (wherein R1, R2 and R3 are hydrogen Or an alkyl group; n represents 0 or an integer of 2 to 20;
Represents an acid. ) An acid addition salt of dihydroxyetheramine represented by the formula: 3. A compound of the general formula (In the formula, Ar represents an optionally substituted aryl group, R ¹ , R ² , and R ³ represent hydrogen or an alkyl group, and n represents an integer of 0 to 20.) base.