JPH0586034A - Hydroxyl group-containing lactam derivative and its production - Google Patents

Abstract

PURPOSE:To obtain a new hydroxyl group-containing lactam derivative capable of providing a highly branched polymer or thermosetting resin even when singly used. CONSTITUTION:A compound of formula I [R is H or 1-20C alkyl; (n) is 2-13], e.g. 7-hydroxymethyl-2-oxohexamethyleneimine. The compound is obtained by oximating a hydroxyl group-containing cyclic ketones (e.g. 2- hydroxymethylcyclohexanone) of formula II and then subjecting the oximated product to ring-enlarging reaction by Beckmann rearrangement. A polyfunctional lactam derivative obtained by reacting the compound of formula II with a polyvalent carboxylic acid or polyvalent isocyanates is useful as a modifier for polyamide resin or curing agent, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel hydroxyl group-containing lactam derivative and a method for producing the same. More specifically, the present invention relates to a hydroxyl group-containing lactam derivative useful as an intermediate raw material for resins suitably used for paints, inks, adhesives, plastic molded articles, etc., and a method for efficiently producing the same. is there.

[0002]

2. Description of the Related Art Conventionally, various monofunctional lactam derivatives have been known to be useful as ring-opening polymerizable monomers. For example, polyamide obtained by ring-opening polymerization of .epsilon.-caprolactam is "6. -Widely used as "nylon". However, such monofunctional lactams are
Due to their monofunctionality, the polymers obtained from them are thermoplastic, linear polymers, which have the disadvantage that by themselves they do not give highly branched polymers or thermosets.

[0003]

The present invention overcomes the disadvantages of the conventional monofunctional lactams, and is capable of obtaining a highly branched polymer or thermosetting resin even when used alone. It was made for the purpose of providing a novel polyfunctional lactam derivative.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies as to a polyfunctional lactam derivative having the above-mentioned preferable properties, and as a result, a hydroxyl group-containing lactam derivative having a specific structure can achieve the object. thing,
Then, it was found that this compound can be efficiently obtained by oxime-forming the corresponding cyclic ketones and then performing a ring expansion reaction by Beckmann rearrangement, and based on this finding, the present invention has been completed. That is, the present invention has the general formula

[0005]

[Chemical 3]

(In the formula, R is a hydrogen atom or has 1 to 20 carbon atoms.
Of the above formula, wherein n is an integer of 2 to 13). According to the present invention, the hydroxyl group-containing lactam derivative has the general formula

[0007]

[Chemical 4]

It can be produced by oximation of a hydroxyl group-containing cyclic ketone represented by the formula (R and n have the same meanings as described above) and then subjecting to ring expansion reaction by Beckmann rearrangement. .. Hereinafter, the present invention will be described in detail.

The hydroxyl group-containing lactam derivative represented by the above-mentioned general formula [1] of the present invention is a hydroxyl group-containing lactam derivative having from 5 to 16 membered rings, as long as this condition is satisfied. Well, although not particularly limited, preferred examples include 5-hydroxymethyl-2-pyrrolidinone and 5- (1-hydroxyethyl)-
2-pyrrolidinone, 6-hydroxymethyl-2-piperidone, 6- (1-hydroxyethyl) -2-piperidone,
7-hydroxymethyl-2-oxohexamethyleneimine, 7- (1-hydroxyethyl) -2-oxohexamethyleneimine, 8-hydroxymethyl-2-oxohexamethyleneimine, 8-hydroxymethyl-2-oxoheptamethylene Imine, 8- (1-hydroxyethyl)-
Examples include 2-oxoheptamethyleneimine, 9-hydroxymethyl-2-oxooctamethyleneimine, 9- (1-hydroxyethyl) -2-oxooctamethyleneimine, and ring alkyl group-substituted products of these compounds. ..

According to the present invention, the hydroxyl group-containing lactam derivative represented by the general formula [1] is oxime-ized with the corresponding hydroxyl group-containing cyclic ketone represented by the general formula [2], and It can be easily produced by carrying out a ring expansion reaction by Beckmann rearrangement. Examples of the hydroxyl group-containing cyclic ketones represented by the general formula [2] include 2-hydroxymethylcyclobutanone, 2- (1-hydroxyethyl) cyclobutanone, 2-hydroxymethylcyclopentanone, 2- (1-hydroxy). Ethyl) cyclopentanone,
2-hydroxymethylcyclohexanone, 2- (1-hydroxyethyl) cyclohexanone, 2-hydroxymethylcycloheptanone, 2- (1-hydroxyethyl)
Examples thereof include cycloheptanone, 2-hydroxymethylcyclooctanone, 2- (1-hydroxyethyl) cyclooctanone, and ring alkyl group-substituted products of these compounds.

The hydroxyl group-containing cyclic ketones represented by the general formula [2] can be prepared by a known method [for example, "Bull Society Chemicals France.
l. Soc. Chim. Fr. ) ”Page 1635 (1954)], the corresponding cyclic ketones and aldehydes such as formaldehyde and acetaldehyde can be easily produced. In the method of the present invention, the hydroxyl group-containing cyclic ketone represented by the general formula [2] is first oxime-converted, but the method of this oximation is not particularly limited, and known methods such as "organic. Synthesis (Org.Sy
nth. ) ”, Volume II, page 313 (1943)]. The hydroxyl group-containing oxime compound thus obtained is subjected to ring expansion reaction by Beckmann rearrangement to be introduced into a hydroxyl group-containing lactam derivative. The Beckmann rearrangement reaction at this time is carried out by a known method [for example, Kyoritsu Shuppan, "Synthesis of Organic Compounds by Small Quantity Method", pages 81 to 93 (1963).
Year))]].

The hydroxyl group-containing lactam derivative represented by the general formula [1] of the present invention can be ring-opening polymerized alone or with other lactams. For example, paints, inks, adhesives, Further, it is useful as an intermediate for a resin used in a plastic molded product or the like. Further, the polyfunctional lactam derivative obtained by reacting the hydroxyl group-containing lactam of the present invention with a polyvalent carboxylic acid or a polyisocyanate is useful as a modifier for a polyamide resin or a curing agent. ..

[0013]

The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. Example 1 (1) Production of 2-hydroxymethylcyclohexanone

[0014]

[Chemical 5]

2-Hydroxymethylcyclohexanone was produced from cyclohexanone according to the reaction formula shown below.
Cyclohexanone 20.0 g (204 mmol) and 36.
After 837 g (102 mmol) of 6 wt% formalin was added to 40 ml of methanol, 0.58 g of potassium hydroxide was added while controlling the temperature at 20 to 25 ° C, and the mixture was stirred for 2 hours. After that, a further 36.6 wt% formalin 8.3
7 g (102 mmol) was added and stirred for 2 hours. After the reaction was completed, the reaction mixture was neutralized with a 5 wt% hydrochloric acid aqueous solution to make it weak base or neutral, concentrated to remove methanol, and then extracted with methylene chloride. Next, the organic layer is dried over anhydrous sodium sulfate, concentrated, and then distilled under reduced pressure to obtain a fraction of 100 to 120 ° C./11 Torr, and then Rf from the origin using column chromatography (silica gel, benzene). The value 0.1 was separated. This product was further distilled under reduced pressure to obtain 55.1 g (43 mmol) of 2-hydroxymethylcyclohexanone. Yield 21.
1% This has a boiling point of 108-110 ° C / 11 Torr
And the characteristic absorption in infrared spectroscopy (IR) and ¹
The chemical shift values in H, ¹³ C nuclear magnetic resonance analysis (NMR) are as follows.

IR (KBr) ν_OH 3400 cm^-1, Ν_{C = 0} 1700 cm^{-1  1}H-NMR (300 MHz, CDCl_Three) Δ (ppm) 1.40-1.58 (1H, m, H-3ax), 1.
58-1.80 (2H, m, H-4ax, 5ax), 1.8
7-1.97 (1H, m, H-4eq), 1.97-2.1
6 (2H, m, H-3, 5), 2.26-2.46 (3H,
m, H-2, 0H), 2.52 (1H, m, H-6), 3.
60 (1H, dd, J = 11.7, 3.9Hz, H-
7) 3.72 (1H, dd, J = 11.7, 7.2Hz,
H-7),¹³ C-NMR (75 MHz, CDCl_Three) Δ (ppm) 24.62 (C-4), 27.40 (C-5), 29.
92 (C-3), 42.11 (C-2), 52.15 (C-
6), 62.70 (C-7), 214.71 (C-1) The positions of carbon atom and hydrogen atom are

[0017]

[Chemical 6]

It is shown by. (2) Oximeation of 2-hydroxymethylcyclohexanone

[0019]

[Chemical 7]

2 obtained in (1) according to the reaction formula shown in
The oximation of hydroxymethylcyclohexanone was carried out. Hydroxylamine hydrochloride 8.11 g (112 mmol) and anhydrous sodium carbonate 5.94 g dissolved in water 70 ml, 2-hydroxymethylcyclohexanone 2.39 g (18.6 mmol) dissolved in tetrahydrofuran (THF) 20 ml Was added dropwise with stirring (if the THF layer was separated, water was added to prevent separation), and then the mixture was stirred at room temperature for 2.0 hours. Next, the reaction mixture was extracted with methylene chloride, the organic layer was dried over anhydrous sodium sulfate, concentrated, and then recrystallized using a methylene chloride-n-hexane mixed solvent.
2-Hydroxymethylcyclohexanone oxime 2.0
7 g (14.5 mmol) were obtained. Yield 77.7% It has a melting point of 86-88 ° C and I
The characteristic absorption of R and the chemical shift values of ¹ H-NMR and ¹³ C-NMR are as shown below.

IR (KBr) ν_OH 3275 cm^-1, Ν_{C = N}1650 cm^{-1  1}H-NMR (300 MHz, CDCl₃) Δ (ppm) 1.43 (3H, m, H-3, 4, 5), 1.80
(4H, m, H-2, 3, 4, 5), 2.38 (1H,
m, H-6), 3.25 (1H, m, H-2), 3.67
(1H, dd, J = 11.4, 4.2Hz, H-7), 3.
76 (1H, dd, J = 11.4, 8.1Hz, H-7),
3.41 (1H, brd, OH-2), 8.19 (1H, b
rd, OH-1),¹³ C-NMR (75 MHz, CDCl₃) Δ (ppm) 23.99 (C-2), 24.70 (C-4), 25.
52 (C-5), 29.56 (C-3), 44.27 (C-
6), 63.93 (C-7), 162.27 (C-1) The positions of the carbon atom and the hydrogen atom are represented by the formula

[0022]

[Chemical 8]

It is shown by. (3) Production of 7-hydroxymethyl-2-oxohexamethyleneimine

[0024]

[Chemical 9]

Beckmann rearrangement reaction of the 2-hydroxymethylcyclohexanone oxime obtained in the above (2) is carried out according to the reaction formula shown in (7) to give 7-hydroxymethyl-2-
Oxohexamethyleneimine was prepared. 0.50 g (3.5 mmol) of 2-hydroxymethylcyclohexanone oxime was gradually added to 3 ml of concentrated sulfuric acid heated at an oil bath temperature of 95 to 100 ° C., and then the oil bath temperature was set to 100 ° C. and stirred for 2 hours. .. After the reaction is completed, the reaction mixture is added to about 20
It was put in ml of water, neutralized with sodium carbonate, extracted with methylene chloride, and the organic layer was dried over anhydrous sodium sulfate and then concentrated. Then, the concentrated residue was recrystallized with a mixed solvent of methylene chloride-n-hexane to give 7-hydroxymethyl-2-oxohexamethyleneimine 0.12.
g was obtained. Yield about 24% Characteristic absorption by IR and ¹ H-NMR, ¹³ C-
The chemical shift values in NMR are as follows.

IR (KBr) ν_OH 3350 cm^-1, Ν_{C = 0}1650 cm^{-1  1}H-NMR (300 MHz, CDCl₃) Δ (ppm) 1.39 (1H, m, H-5), 1.55 (2H,
m, H-3, 4), 1.70 (1H, m, H-5), 1.8
6 (1H, m, H-3), 2.02 (1H, m, H-4),
2.46 (2H, m, H-2), 3.47 (1H, m, H-
6) 3.57 (1H, dd, J = 11.4, 7.8Hz,
H-7), 3.67 (1H, dd, J = 11.4, 3.8H
z, H-7), 3.85 (1H, brd, OH), 7.65
(1H, brd, NH)¹³ C-NMR (75 MHz, CDCl₃) Δ (ppm) 22.98 (C-3), 29.38 (C-4), 31.
67 (C-5), 36.85 (C-2), 55.88 (C-
6), 65.29 (C-7), 179.39 (C-1) The positions of the carbon atom and the hydrogen atom are represented by the formula

[0027]

[Chemical 10]

It is shown by.

[0029]

INDUSTRIAL APPLICABILITY The hydroxyl group-containing lactam derivative of the present invention can form a hyperbranched polymer or a thermosetting polymer alone or by ring-opening polymerization with other lactams. It is useful as an intermediate raw material for resins suitably used for adhesives, plastic molded products, etc., and is also useful as a modifier or curing agent for polyamide resins by reacting with polycarboxylic acids or polyisocyanates. It is also possible to give various polyfunctional lactam derivatives. Further, according to the method of the present invention, the hydroxyl group-containing lactam derivative can be efficiently produced from the corresponding hydroxyl group-containing cyclic ketones.

Claims (2)

[Claims] 1. A general formula: (Wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, n is an integer of 2 to 13), and a hydroxyl group-containing lactam derivative. 2. A general formula: (Wherein R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, n is an integer of 2 to 13), the hydroxyl group-containing cyclic ketone is oxime-ized, and then a ring expansion reaction is carried out by Beckmann rearrangement. The method for producing a hydroxyl group-containing lactam derivative according to claim 1, wherein