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EXAMPLE 1 A 1l reactor is charged with 34 g (0.3 mole) of azacycloheptane-2-one, 112 g (0.45 mole) of dodecyl bromide, 300 g of toluene, 3.4 g (3.3 mole percent based on the azacycloheptane-2-one) of crystalline tetrabutylammonium hydrogensulfate (TBAHS) and 90 g (2.25 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. After the mixture was cooled to 40° C., 135 g of water was added to the mixture, followed by stirring at 40° C. for 30 minutes. The oil layer was separated and the oil layer thus obtained was subjected to distillation, giving 84.0 g of 1-dodecylazacycloheptane-2-one having a boiling point of 195° to 200° C./3 mmHg (yield of 99.6percent based on the azacycloheptane-2-one), and also 0.8 g of dodecyl ether (yield of 1.0percent based on the dodecyl bromide).
95%
With sodium hydroxide In toluene
EXAMPLE 3 A 1l reactor was charged with 57 g (0.5 mole) of azacycloheptane-2-one, 125 g (0.5 mole) of dodecyl bromide, 182 g of toluene, 3.2 g (2 mole percent) of crystalline tetrabutylammonium bromide (TBAB) and 60 g (1.5 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. The same aftertreatment as in Example 1 was repeated, giving 133.5 g of 1-dodecylazacycloheptane-2-one (yield of 95.0percent) and 0.7 g of dodecyl ether (yield of 0.8percent)
92.8%
With sodium hydroxide; tetrabutylammomium bromide; potassium carbonate In cyclohexane
EXAMPLE 1 Preparation of 1-n-dodecylazacycloheptan-2-one at a bath temperature of 55° C. 117 g of caprolactam (1.033 mole), 10 g of tetrabutylammonium bromide (0.03 mole), 100 g of anhydrous potassium carbonate (0.7 mole, dried for 2 hrs at 120 C.), 100 g of pulverized sodium hydroxide (2.5 mole), and 1 L of cyclohexane were placed in a flask equipped with a funnel, reflux condenser and a mechanical stirrer. To this mixture were added dropwise a solution of 250 ml of 1-bromododecane (1.033 mole) and 250 ml of cyclohexane with vigorous stirring over one-half hour at a bath temperature of 55° C. The stirring was continued; in the meanwhile thin-layer chromatography was used to monitor the course of the reaction, and it was found that the reaction was completed after 7 hours. The reaction mixture was then cooled to room temperature and filtered. The filtrate was washed with water (3*500 ml) to remove remaining caprolactam. The organic phase was dried over anhydrous magnesium sulfate. The filtrate was evaporated using a rotary film evaporator to remove cyclohexane (which can be used again), and the residue was distilled at reduced pressure to yield 270 g of colorless, odorless, transparent liquid product (yield: 92.8percent), b,p.200-201 C/0.7 mmHg.
Reference：
[1] Patent: US4812566, 1989, A,
[2] Patent: US4812566, 1989, A,
[3] Patent: US4973688, 1990, A,
[4] JAOCS, Journal of the American Oil Chemists' Society, 1996, vol. 73, # 7, p. 847 - 850
[5] Journal of Pharmaceutical Sciences, 1993, vol. 82, # 2, p. 214 - 219
[6] Journal of Pharmaceutical Sciences, 1989, vol. 78, # 9, p. 738 - 741
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Reference：
[1] Patent: US4422970, 1983, A,
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Reference：
[1] Patent: US4812566, 1989, A,
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[1] Patent: US4692523, 1987, A,
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Reference：
[1] Patent: US4310525, 1982, A,
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Reference：
[1] Patent: US5986092, 1999, A,
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Reference：
[1] Patent: US4525199, 1985, A,
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Reference：
[1] JAOCS, Journal of the American Oil Chemists' Society, 1996, vol. 73, # 7, p. 847 - 850
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Reference：
[1] Journal of Organic Chemistry, 1953, vol. 18, p. 1087,1088
EXAMPLE 1 A 1l reactor is charged with 34 g (0.3 mole) of azacycloheptane-2-one, 112 g (0.45 mole) of dodecyl bromide, 300 g of toluene, 3.4 g (3.3 mole percent based on the azacycloheptane-2-one) of crystalline tetrabutylammonium hydrogensulfate (TBAHS) and 90 g (2.25 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. After the mixture was cooled to 40° C., 135 g of water was added to the mixture, followed by stirring at 40° C. for 30 minutes. The oil layer was separated and the oil layer thus obtained was subjected to distillation, giving 84.0 g of 1-dodecylazacycloheptane-2-one having a boiling point of 195° to 200° C./3 mmHg (yield of 99.6percent based on the azacycloheptane-2-one), and also 0.8 g of dodecyl ether (yield of 1.0percent based on the dodecyl bromide).
95.0%
With sodium hydroxide; In toluene;
EXAMPLE 3 A 1l reactor was charged with 57 g (0.5 mole) of azacycloheptane-2-one, 125 g (0.5 mole) of dodecyl bromide, 182 g of toluene, 3.2 g (2 mole percent) of crystalline tetrabutylammonium bromide (TBAB) and 60 g (1.5 moles) of flaky sodium hydroxide. This heterogeneous mixture was stirred at 50° C. for 10 hours. The same aftertreatment as in Example 1 was repeated, giving 133.5 g of 1-dodecylazacycloheptane-2-one (yield of 95.0percent) and 0.7 g of dodecyl ether (yield of 0.8percent)
92.8%
With sodium hydroxide; tetrabutylammomium bromide; potassium carbonate; In cyclohexane;
EXAMPLE 1 Preparation of 1-n-dodecylazacycloheptan-2-one at a bath temperature of 55° C. 117 g of caprolactam (1.033 mole), 10 g of tetrabutylammonium bromide (0.03 mole), 100 g of anhydrous potassium carbonate (0.7 mole, dried for 2 hrs at 120 C.), 100 g of pulverized sodium hydroxide (2.5 mole), and 1 L of cyclohexane were placed in a flask equipped with a funnel, reflux condenser and a mechanical stirrer. To this mixture were added dropwise a solution of 250 ml of 1-bromododecane (1.033 mole) and 250 ml of cyclohexane with vigorous stirring over one-half hour at a bath temperature of 55° C. The stirring was continued; in the meanwhile thin-layer chromatography was used to monitor the course of the reaction, and it was found that the reaction was completed after 7 hours. The reaction mixture was then cooled to room temperature and filtered. The filtrate was washed with water (3*500 ml) to remove remaining caprolactam. The organic phase was dried over anhydrous magnesium sulfate. The filtrate was evaporated using a rotary film evaporator to remove cyclohexane (which can be used again), and the residue was distilled at reduced pressure to yield 270 g of colorless, odorless, transparent liquid product (yield: 92.8percent), b,p.200-201 C/0.7 mmHg.
COMPARISON EXAMPLE 1 The same procedure as in Example 1 was repeated with the exception of using 360 g (4.50 moles) of a 50percent aqueous solution of sodium hydroxide in place of the flaky sodium hydroxide used in Example 1. This heterogeneous mixture was stirred at 50° C. for 30 hours. The same aftertreatment as in Example 1 was performed, giving 69.4 g of 1-dodecylazacycloheptane-2-one (yield of 82.3percent based on the azacycloheptane-2-one) and 10.0 g of dodecyl ether (yield of 12.6percent based on the dodecyl bromide).
The following may be mentioned as examples of N-alkyl-lactams of the formula (II):N-dodecyl-caprolactamN-decyl-caprolactamN-octyl-caprolactamN-dodecyl-pyrrolidoneN-decyl-pyrrolidoneN-octyl-pyrrolidoneN-dodecyl-valerolactamN-decyl-valerolactamN-octyl-valerolactam.
Examples of N-alkyl-lactams of the formula (I) which may be mentioned are:N-dodecyl-caprolactamN-decyl-caprolactamN-octyl-caprolactamN-dodecyl-pyrrolidoneN-decyl-pyrrolidoneN-octyl-pyrrolidoneN-dodecyl-valerolactamN-decyl-valerolactamN-octyl-valerolactam.
Examples which may be mentioned of N-alkyl-lactams of the formula (I) are:N-dodecyl-caprolactamN-decyl-caprolactamN-octyl-caprolactamN-dodecyl-pyrrolidoneN-decyl-pyrrolidoneN-octyl-pyrrolidoneN-dodecyl-valerolactamN-decyl-valerolactamN-octyl-valerolactam.
EXAMPLE 2 N-n-dodecylcaprolactam Reaction analogous to Example 1; 300 ml of 1,2-dimethoxyethane are used as solvent in place of 300 ml of toluene. Boiling point (0.15 mm) 175°-176° C.; yield 39.5 g.
0.8%
EXAMPLE 4 The same reaction as in Example 3 was repeated with the exception of changing the reaction temperature of Example 3 to 70° C. and the reaction time thereof to 5 hours, followed by the same aftertreatment, giving 134.2 g of 1-dodecylazacycloheptane-2-one (yield of 95.5percent) and 0.7 g of dodecyl ether (yield of 0.8percent).
With sodium hydroxide; tetrabutylammomium bromide;
COMPARATIVE EXAMPLE 6 Preparation of N-dodecylcaprolactam in the presence of methyl tert-butyl ether as solvent. 81 g of methyl tert-butyl ether, 17.8 g (0.157 mol) of caprolactam, 18.9 g (0.47 mol) of pearl sodium hydroxide, 2.03 g (0.006 mol) of tetrabutylammonium bromide and 37.4 g (0.15 mol) of dodecyl bromide are introduced into a 250-ml reactor equipped and treated as in Example 1. The mixture is stirred and heated at 60° C. for 9 hours 30 min. It is then treated as in Comparative Examples 2 and 3. 34.5 g of crude N-dodecylcaprolactam are obtained with a purity of 86percent. The chemical yield of N-dodecylcaprolactam is 72percent.
EXAMPLE 3 N-n-dodecylcaprolactam 3.1 g (0.05 mol) of sodium oxide (Na2 O) are suspended in 150 ml of 1,2-dimethoxyethane, and then 18.5 g (0.1 mol) of N-trimethylsilylcaprolactam are added. The reaction mixture is stirred at 50° C. for two hours, during which the voluminous precipitate of the sodium salt of the caprolactam forms. Then 24.9 g (0.1 mol) of n-dodecyl bromide are added, and the mixture is stirred and heated under reflux for 20 hours. The working-up is carried out as indicated in Example 1. Boiling point (0.15 mm) 175°-176° C.; yield 20.8 g.
With phosphorus pentachloride; bromine; In dichloromethane; chloroform;
A. Preparation of 3-Bromo-1-dodecylazacycloheptan-2-one To a cold solution of 107 g (0.38 mol) of 1-dodecylazacycloheptan-2-one, in CHCl3 was added 159.7 g (0.77 mol) of PCl5, keeping the temperature between 1°-4° C. After 2 hours, a solution of 123.3 g (0.77 mol) of bromine in CHCl3 was added, and the mixture was stirred for 18 hours at room temperature. After removing the solvent and excess bromine by vacuum distillation, the residue was dissolved in CH2 Cl2, washed with sat. Na2 S2 O5, dried over MgSO4, and concentrated in vacuo to give a crude oil. Purification by flash chromatography (silica gel; 1:1 ether/petroleum ether V/V) gave pure product.
EXAMPLE I Preparation of 1-dodecylazacycloheptan-2-one The operation was carried out under nitrogen. In a 5 liter 3-neck flask equipped with an efficient condenser, an additional funnel and a mechanical stirrer was placed 91.8 g (1.91 M) of 50percent sodium hydride (dispersed in mineral oil). This was mixed with 600 ml of pet. ether (30-60), the mixture was momentarily stirred and then sodium hydride was allowed to settle. Most of the petroleum ether was pipetted out and 1500 ml of toluene was added to the NaH. To this was added under stirring and dropwise a solution of 180 g (1.59 M) of azacycloheptan-2-one in 800 ml of toluene. Foaming, hydrogen evaluation and formation of sodium salt took place. After the addition, the reaction mixture was refluxed for two hours and then cooled to room temperature. A solution of 398 g (1.59 M) of 1-bromododecane in 100 ml of toluene was added dropwise under stirring. Upon completion of the addition, the reaction mixture was refluxed for 45 hours. After cooling, the contents were filtered through celite and the filtrate was concentrated to a yellow oil. This was distilled at 155° to 160°/100mu to give 402 g (89percent) of a clear colorless oil. Redistillation at 155° to 160°/100mu gave 396 g (88.5percent) of pure 1-dodecylazacycloheptan-2-one.
EXAMPLE 3 Preparation of 1-dodecylazacycloheptan-2-one with tricaprylylmethylammonium chloride (aliquat 336.(R).) as catalyst. To a solution of 2.5 g (22.09 millimole) of azacycloheptan-2-one and 10 ml (41.64 millimole) of 1-bromododecane in 50 ml of toluene was added 50 ml of 50percent sodium hydroxide solution followed by 0.45 g (1.1 millimole) (0.05 mole percent) of tricaprylylmethylammonium chloride (Aliquat 336.(R).). The mixture was vigorously stirred with a mechanical stirrer at 40°-50° C. for 120 hrs. After cooling to room temperature the organic layer was separated, the aqueous layer was extracted with 2*100 ml of ether and the combined organic solution was washed twice with a saturated sodium chloride solution. After drying over anhydrous magnesium sulfate the filtrate was concentrated and the residue was fractionally distilled. 3.62 g forerun was excess 1-bromododecane (which can be recycled). The desired compound, 1-dodecylazacycloheptan-2-one distilled at 145°-155°/0.2 mm. Yield 6.15 g (99.2percent).
COMPARISON EXAMPLE 2 A 46.0 g quantity of 1-dodecylazacycloheptane-2-one (yield of 54.6percent based on the azacycloheptane-2-one) and 5.0 g of dodecyl ether (yield of 6.3percent based on the dodecyl bromide) were produced by conducting the same reaction and the same aftertreatment as in Comparison Example 1 with the exception of changing the reaction time of COMPARISON EXAMPLE 1 to 10 hours.
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Yield
Reaction Conditions
Operation in experiment
60 g (80%)
STR23 Following Example 10, 15.3 g of 50percent sodium hydride-mineral oil dispersion (7.65 g NaH, 0.319M), 30 g (0.266M) of azacycloheptan-2-one and 66.1 g (0.265M) of 1-bromododecane on 20 hours reflux gave 60 g (80percent) of colorless product; b.p. 175°-180°/0.3 mm.
EXAMPLE 7 The same reaction as in Example 4 was repeated with the exception of using 102 g (0.5 mole) of dodecyl chloride in place of the dodecyl bromide and changing the reaction time of Example 4 to 10 hours, followed by the same aftertreatment, giving 133.8 g of 1-dodecylazacycloheptane-2-one (yield of 95.2percent) and 0.4 g of dodecyl ether (yield of 0.5percent).
Stage #1: Azone With bis(triphenylphosphine)carbonyliridium(I) chloride; 1,1,3,3-Tetramethyldisiloxane In dichloromethane at 20℃; for 0.5h;
Stage #2: 4-toluenesulfonyl azide In dichloromethane at 20℃; for 3h; chemoselective reaction;
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