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Structure of 112-18-5 * Storage: {[proInfo.prStorage]}
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
A mixture of a 38percent aqueous solution of dimethylamine (12.5 mL, 93.8 mmol) and dodecyl bromide (11.7 g, 46.9 mmol) in benzene (15 mL) was stirred at 20—25 °C for 20 h. Then, a 50percent aqueous solution of NaOH (1.9 g, 46.9 mmol) was added to the reaction mixture, and the resulting mixture was evaporated in vacuo. The residue was dissolved in CHCl3 (20 mL), the formed precipitate was filtered off, and the filtrate was evaporated in vacuo. According to the 1H NMR spectral data, the isolated mixture contained amine 6a (4.1 g, 40percent), N,N-didodecyl-N,N-dimethylammonium bromide (4.9 g, 46percent), and unreacted dodecyl bromide (1.7 g, 14percent).
Reference：
[1] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[2] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
2
[ 112-18-5 ]
[ 143-15-7 ]
[ 3282-73-3 ]
Reference：
[1] Chemical Communications, 2006, # 44, p. 4575 - 4577
[2] Journal of Organic Chemistry, 1984, vol. 49, # 20, p. 3774 - 3778
[3] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1987, p. 541 - 546
[4] Journal of Physical Chemistry, 1983, vol. 87, # 4, p. 538 - 540
[5] Bulletin of the Chemical Society of Japan, 2003, vol. 76, # 10, p. 1903 - 1910
[6] Patent: WO2005/97729, 2005, A2, . Location in patent: Page/Page column 49-50; 56-57
3
[ 112-18-5 ]
[ 3926-62-3 ]
[ 683-10-3 ]
Yield
Reaction Conditions
Operation in experiment
35%
at 90 - 95℃; for 1 h;
General procedure: A mixture of amine 6a,c—h (6 mmol) and alkylchloride (6 mmol) in water (2—3 mL) was stirred at 60—95 °C for 0.3—4 h and then evaporated in vacuo. The residue was purified by column chromatography on silica gel in a CHCl3—MeOH (10 : 1) system or by recrystallization. The reaction conditions in each particular case, yields, and physicochemical parameters of quaternary ammonium compounds 1a—g, 2a—c, and 5a—c are presentedin Table 3. The data of the 1H NMR spectra are given in Table 5.
Reference：
[1] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[2] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
[3] Kogyo Kagaku Zasshi, 1957, vol. 60, p. 1294,1296[4] Chem.Abstr., 1959, p. 13731
[5] Yakugaku Zasshi, 1948, vol. 63, p. 592[6] Chem.Abstr., 1951, p. 5100
[7] DRP/DRBP Org.Chem.,
[8] Patent: US2082275, 1935, ,
[9] Journal of Pharmacy and Pharmacology, 1963, vol. 15, p. 422 - 431
[10] Journal of Physical Chemistry, 1988, vol. 92, # 2, p. 440 - 445
[11] Patent: CN205575966, 2016, U, . Location in patent: Paragraph 0013; 0014; 0015; 0016; 0017; 0018
[12] DRP/DRBP Org.Chem.,
4
[ 112-18-5 ]
[ 7748-25-6 ]
[ 683-10-3 ]
Yield
Reaction Conditions
Operation in experiment
96%
at 80℃; for 2 h;
General procedure: An acetonitrile mixture (15 ml) containing the long alkyl bromoalkane(15 mmol) or the potassium salt of chloroacetic acid(11.25 mmol) was placed in a semi-automated system EasyMax 102(Mettler Toledo) equipped with a 50 mL glass reactor, magneticstirring bar and ReactIR probe. After 5 min of stirring at 80 C, the appropriate tertiary amine (15 mmol) or dimethyldodecylamine(11.25 mmol) was quickly added. The reaction was carried out at 80 C and the optimal time of the reaction was determined byReactIR iC15 (Mettler Toledo) equipped with a MCT detector anda 9.5 mm AgX probe with a diamond tip. Data were sampled from2500 to 650 cm1 with 8 cm1 resolution and processed by iCIR 4.3software. Upon completion, the mixture was cooled to 20 C andthe solvent was removed by rotary evaporator under vacuum. Next,the obtained precursors were purified by washing repeatedly with acetone and dried under reduced pressure (5 mbar) at 60 C for24 h.
Reference：
[1] Patent: US2013/66108, 2013, A1, . Location in patent: Paragraph 0139
[2] Patent: CN105777566, 2016, A, . Location in patent: Paragraph 0011-0014
6
[ 112-18-5 ]
[ 95578-02-2 ]
[ 3868-21-1 ]
[ 683-10-3 ]
Reference：
[1] Nucleosides, Nucleotides and Nucleic Acids, 2009, vol. 28, # 10, p. 911 - 923
7
[ 112-18-5 ]
[ 105-39-5 ]
[ 683-10-3 ]
Reference：
[1] Nippon Nogei Kagaku Kaishi, 1959, vol. 33, p. 362,364[2] Chem.Abstr., 1963, vol. 58, p. 4447
8
[ 111-24-0 ]
[ 112-18-5 ]
[ 18464-25-0 ]
Reference：
[1] Molecules, 2011, vol. 16, # 1, p. 319 - 335
[2] Bioorganic and Medicinal Chemistry Letters, 2014, vol. 24, # 24, p. 5824 - 5828
[3] Pharmaceutical Chemistry Journal, 1968, # 5, p. 247 - 250[4] Khimiko-Farmatsevticheskii Zhurnal, 1968, # 5, p. 15 - 18
[5] Canadian Journal of Chemistry, 2010, vol. 88, # 2, p. 124 - 134
9
[ 74-87-3 ]
[ 112-18-5 ]
[ 112-00-5 ]
Reference：
[1] Journal of Organic Chemistry, 1947, vol. 12, p. 518
10
[ 112-18-5 ]
[ 112-52-7 ]
[ 3401-74-9 ]
Reference：
[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1987, p. 541 - 546
[2] Journal of Physical Chemistry, 1982, vol. 86, # 6, p. 992 - 998
11
[ 112-18-5 ]
[ 100-44-7 ]
[ 139-07-1 ]
Yield
Reaction Conditions
Operation in experiment
80%
at 60 - 65℃; for 0.3 h;
General procedure: Alkylation of tertiary amines 6a,c—h in water (general procedure). A mixture of amine 6a,c—h (6 mmol) and alkylchloride (6 mmol) in water (2—3 mL) was stirred at 60—95 for 0.3—4 h and then evaporated in vacuo. The residue was purified by column chromatography on silica gel in a CHCl3—MeOH (10 : 1) system or by recrystallization. The reaction conditions in each particular case, yields, and physicochemical parameters of quaternary ammonium compounds 1a—g, 2a—c, and 5a—c are presentedin Table 3. The data of the 1H NMR spectra are given in Table 5.
Reference：
[1] Russian Chemical Bulletin, 2014, vol. 63, # 11, p. 2445 - 2454[2] Izv. Akad. Nauk, Ser. Khim., 2014, # 11, p. 2445 - 2454
[3] Yakugaku Zasshi, 1943, vol. 63, p. 589[4] Chem.Abstr., 1951, p. 5100
[5] Journal of Colloid Science, 1946, vol. 1, p. 385
[6] Pharmaceutical Chemistry Journal, 1974, vol. 8, # 10, p. 602 - 604[7] Khimiko-Farmatsevticheskii Zhurnal, 1974, vol. 8, # 10, p. 21 - 24
[8] Pharmaceutical Chemistry Journal, 1984, vol. 18, # 11, p. 784 - 787[9] Khimiko-Farmatsevticheskii Zhurnal, 1984, vol. 18, # 11, p. 1344 - 1348
[10] Physical Chemistry Chemical Physics, 1999, vol. 1, # 8, p. 1957 - 1964
[11] Journal of Physical Organic Chemistry, 1999, vol. 12, # 4, p. 325 - 332
[12] Revue Roumaine de Chimie, 2001, vol. 46, # 1, p. 49 - 53
[13] Revue Roumaine de Chimie, 2001, vol. 46, # 1, p. 49 - 53
[14] Antimicrobial Agents and Chemotherapy, 2002, vol. 46, # 5, p. 1469 - 1474
[15] Patent: CN106431995, 2017, A, . Location in patent: Paragraph 0028; 0029; 0045; 0046
[16] Patent: CN106946716, 2017, A, . Location in patent: Paragraph 0016; 0021
[17] Patent: CN106916071, 2017, A, . Location in patent: Paragraph 0016; 0021; 0022
A mixture of N, N-dimethyldodecylamine (50 mmol) and 1, 3-propanesultone (52mmol) in ethanol (20 mL)was stirred at roomtemperaturefor 24 h. On completion, this reaction system was placed in anice-water bath and cooled to 0–5 °C, the resulting precipitate was filtered,washed with diethyl ether, and dried at 65 °C under a vacuumfor 8 h to afford precursor zwitterionic salt (1) in a yield of 95percent.
Reference：
[1] Monatshefte fur Chemie, 2009, vol. 140, # 11, p. 1325 - 1329
[2] Catalysis Communications, 2015, vol. 69, p. 5 - 10
[3] Journal of Surfactants and Detergents, 2011, vol. 14, # 1, p. 31 - 35
[4] Synthesis, 2002, # 16, p. 2431 - 2439
[5] Journal of Physical Chemistry, 1984, vol. 88, # 25, p. 6357 - 6362
[6] Berichte der Bunsen-Gesellschaft, 1989, vol. 93, p. 180 - 183
[7] Journal of Heterocyclic Chemistry, 2011, vol. 48, # 2, p. 468 - 472
[8] RSC Advances, 2015, vol. 5, # 40, p. 31772 - 31786
[9] Journal of Surfactants and Detergents, 2016, vol. 19, # 4, p. 813 - 822
16
[ 24308-28-9 ]
[ 112-18-5 ]
[ 14933-08-5 ]
Reference：
[1] Catalysis Science and Technology, 2013, vol. 3, # 4, p. 1102 - 1107
General procedure: A mixture of amine 6a,c-h (6 mmol) and alkylchloride (6 mmol) in water (2-3 mL) was stirred at 60-95 C for 0.3-4 h and then evaporated in vacuo. The residue was purified by column chromatography on silica gel in a CHCl3-MeOH (10 : 1) system or by recrystallization. The reaction conditions in each particular case, yields, and physicochemical parameters of quaternary ammonium compounds 1a-g, 2a-c, and 5a-c are presentedin Table 3. The data of the 1H NMR spectra are given in Table 5.
at 80℃; for 6.0h;Large scale;
Chloroacetic acid was added to D101 in a metered manner,And then the amount of sodium hydroxide and other substances in the solution of chloroacetic acid to pH 8,The sodium salt of chloroacetic acid was obtained.And then add the amount of such substancesDodecyl dimethyl tertiary amine,The reaction was carried out at 80 C for 6 hours,Products 1.
With dihydrogen peroxide In water at 100℃; for 6h;
97%
With 2,2,2-Trifluoroacetophenone; dihydrogen peroxide; acetonitrile In <i>tert</i>-butyl alcohol at 20℃; for 18h; Green chemistry; chemoselective reaction;
96%
With dihydrogen peroxide In methanol at 70℃; for 16h;
2.2. Synthesis of N-Oxide (NO) derivatives
General procedure: In a 100 mL round bottom flask equipped with a condenser and a dropping funnel, 2.5 mL (7.5 mmol) dimethylalkylamine were introduced in methanol (10 mL). The reaction mixture was refluxed for one hour, and 1.15 mL (11.25 mmol, 1.5 eq) of hydrogen peroxide (30 wt.%) was added dropwise. The reaction was heated at 70 °C under vigorous stirring for 15 h, and was followed by Thin Layer Chromatography. The solvent was removed and the product was dried in a lyophilizer for 24 h. NO12 (dimethyldodecylamine oxide): White solid, 96% yield, Rf=0.65 (AcOEt), NMR 1H (400 MHz, CDCl3, 25 °C, TMS): δ=0.81 (t, 3H),1.19 (m, 16H), 1.27 (m, 2H), 1.79 (m, 2H), 3.14 (s, 6H), 3.20 (m, 2H);NMR 13C (100 MHz, CDCl3, 25 °C, TMS): δ=14.09, 22.65,23.94,26.64, 29.29-29.56,31.87, 58.30, 71.74, Tf=120 °C.
96%
With dihydrogen peroxide In ethanol at 50℃; for 24h;
N,N-dimethyldodecan-1-amine oxide (33) C12-Oxide [1b]
To a 100 mL round-bottom flask containing a magnetic stirring barwas added CH3(CH2)11N(CH3)2 (10, 5 mmol, 1.07 g, 1 eq.), and ethanol(50 mL). The reaction mixture was stirred evenly and heated to 50 C.Then, hydrogen peroxide (15 mmol, 1.70 g, 3.0 eq.) was slowly droppedin and the mixture was stirred at 50 C for 24 h. The organic extract wasconcentrated by rotary evaporation under vacuum. The final productwas obtained as a white viscous solid (1.10 g, 96%). 1H NMR (400 MHz,CD3OD) δ 3.23 (t, J = 8.4 Hz, 2H), 3.11 (s, 6H), 1.85 - 1.75 (m, 2H), 1.40- 1.20 (m, 18H), 0.86 (t, J = 6.8 Hz, 3H). IR (film) v/cm 1: 3372.9,2921.8, 2852.3, 1652.2, 1467.3, 1378.0, 965.7, 924.8, 773.8, 721.0
95%
With oxygen In methanol; water at 100℃; for 64h; E(a), ΔS(excit.); other tertiary amines, var. pressure of oxygen and reaction temp.;
95%
With oxygen In methanol; water at 100℃; for 64h;
85%
With 1,3-dimethyl-5-ethyl-5,10-dihydroalloxazine; dihydrogen peroxide In methanol; water for 8h; Ambient temperature;
81%
With dihydrogen peroxide In methanol; water
With oxygen In ethanol; water at 80 - 115℃; activation energy;
With dihydrogen peroxide In isopropyl alcohol at 75℃; other cyclic amines; var. temp., var. solvent;
With dihydrogen peroxide In d(4)-methanol; water time dependence; rate enhancement in the presence of 1,3-dimethyl-5-ethyl-5,10-dihydroalloxazine; effect of amount of reagent;
With ethanol; dihydrogen peroxide at 60℃;
With dihydrogen peroxide
With methanol; dihydrogen peroxide
With tert.-butylhydroperoxide In benzene
With dihydrogen peroxide at 0℃; for 2h;
With dihydrogen peroxide
With water In ethanol; water at 75℃; for 3h;
With dihydrogen peroxide In isopropyl alcohol at 75℃;
With dihydrogen peroxide In water
3 EXAMPLE 3
EXAMPLE 3 This is a comparative example conducted with CO2 but without the aluminum coupon. In a glass reaction flask was placed 250 g dodecyldimethylamine. The amine was heated to 65° C. under a carbon dioxide atmosphere and 86 g of 50 percent aqueous hydrogen peroxide and 584 ml of water were added over a 1-hour period. Stirring was continued for 2 hours at 65° C. Conversion to dodecyldimethylamine oxide was essentially complete. The product was analyzed as in Example 1. The analysis showed 96 ppb N-nitroso dimethylamine.
With dihydrogen peroxide In water
3 Example 3
Example 3 This is a comparative example conducted with CO2 but without the titanium coupon. In a glass reaction flask was placed 250 g dodecyldimethylamine. The amine was heated to 65°C under a carbon dioxide atmosphere, and 86 g of 50 percent aqueous hydrogen peroxide and 584 ml of water were added over a 1-hour period. Stirring was continued for 2 hours at 65°C. Conversion to dodecyldimethylamine oxide was essentially complete. The product was analyzed as in Example 1. The analysis showed 96 ppb N-nitrosodimethylamine.
With dihydrogen peroxide In water at 90℃; for 9h;
5; 15; 16; 17
EXAMPLE 15 The reaction product obtained in Example 1 was subjected to purification and fractionation procedure by distillation, thereby obtaining lauryl dimethyl amine (purity as measured by gas chromatography: 99.9%). A 1 L four-necked flask equipped with a thermometer, a stirrer, a cooling tube and a dropping funnel was charged with 258.8 g of the thus obtained lauryl dimethyl amine (weight-average molecular weight: 215.7) and 439.8 g of ion-exchanged water, and the contents of the flask were heated to 90°C. Thereafter, 91.9 g of a 45% hydrogen peroxide aqueous solution was dropped into the flask over 1 h. Further, the contents of the flask were stirred at 90°C for 8 h, thereby obtaining a reaction product containing about 35% of lauryl dimethyl amine oxide. The hue and odor of the thus obtained product were evaluated immediately after production thereof and after preserving the product at 60°C. The results are shown in Table 5.; EXAMPLES 16 AND 17 The same procedure as in Example 15 was repeated except for using the reaction products respectively obtained in Examples 4 and 8 in place of the reaction product obtained in Example 1, thereby respectively obtaining reaction products containing lauryl dimethyl amine oxide. The hue and odor of the thus obtained products were evaluated immediately after production thereof and after preserving the products at 60°C. The results are shown in Table 5.
With water; dihydrogen peroxide at 90℃; for 9h;
12; 13; 4
The reaction product obtained in Example 1 was subjected to purification and fractionation procedure by distillation, thereby obtaining lauryl dimethyl amine (purity as measured by gas chromatography: 99.9%). A l L four-necked flask equipped with a thermometer, a stirrer, a cooling tube and a dropping funnel was charged with 259 g of the thus obtained lauryl dimethyl amine (weight- average molecular weight^ 215.7) and 440 g of ion-exchanged water, and the contents of the flask were heated to 900C. Thereafter, 92 g of a 45% hydrogen peroxide aqueous solution was dropped into the flask over 1 h. Further, the contents of the flask were stirred at 900C for 8 h, thereby obtaining a reaction product containing about 35% of lauryl dimethyl amine oxide. The hue and odor of the thus obtained product were evaluated immediately after production thereof and after preserving the product at 600C. The results are shown in Table 4.; EXAMPLE 13The same procedure as in Example 12 was repeated except for using the reaction product obtained in Example 3 in place of the reaction product obtained in Example 1, thereby obtaining a reaction product containing lauryl dimethyl amine oxide. The hue and odor of the thus obtained product were evaluated immediately after production thereof and after preserving the product at 6O0C. The results are shown in Table 4.; COMPARATIVE EXAMPLE 4 The same procedure as in Example 12 was repeated except for using the reaction product obtained in Comparative Example 3 in place of the reaction product obtained in Example 1, thereby obtaining a reaction product containing lauryl dimethyl amine oxide as aimed. The hue and odor of the thus obtained product were evaluated immediately after production thereof and after preserving the product at 600C. The results are shown in Table 4.Meanwhile, the hue and odor of the respective reaction products were evaluated by the following methods. (Evaluation of Hue) The sample was placed in a glass container for measurement to measure a hue thereof using a tintometer "Lovibond Tintometer PFX995". (Evaluation of Odor)The sample was subjected to sensory test by expert panelists to evaluate an odor thereof according to the following 4 ratings A, B, C and D. Evaluation CriteriaA: ExcellentB: Good C: Slightly poor D'- Poor
With dihydrogen peroxide In ethanol at 65 - 70℃; for 6h;
Synthesis of N-oxides (AO-12, AO-18, MO, MO-12):
General procedure: N-oxides can besynthesizedwith different procedures [47,48]. In thiswork,we useda simple and cheap procedure based on the use of hydrogen peroxide:the corresponding amine was put at 65-70 °C in EtOH with 1.5equivalents of H2O2. After 6 h MnO2 was added to destroy H2O2 excess,the liquidwas filtered and the solventwas removed under vacuum.The resulting semi-solids were recrystallized twice in acetone/Et2Omixtures.
With hydrogen In 1,2-dimethoxyethane at 120℃; for 1h; Autoclave; Molecular sieve;
99%
With hydrogen In 1,2-dimethoxyethane at 120℃; for 1h; Autoclave; Molecular sieve;
1-20 Examples 10-12: Hydrogenation of N, N-dimethyl Laurylamide
Hydrogenation was performed in a Top-Industry reaction system at 40 bar H2pressure at a given temperature as specified in Table 3 in the presence of 1.0 g VyOx/Rh/Al2O3type catalyst with Rh/V molar ratio of 1/1 prepared in Example 1 for 1 hour. The hydrogenation was carried out under diluted condition using 50 ml dimethyl ethane (DME) as a solvent for 5.0 mmol N, N-dimethyl laurylamide. 1.0 g molecular Sievewas used as water scavenging agent.[0179]In particular, N, N-dimethyl laurylamide in dimethoxy ethane (DME) was introduced in the reactor, followed by the addition of 0.15 g of catalyst. After closing the reactor, the system was purged at least 5 times with pure hydrogen, and then, pressurized at the desired H2pressure. Finally, the autoclave was placed inside a heated aluminum block, preheated at the given reaction temperature. After finishing the reaction, the reactor was cooled down with water, depressurized and opened to immediately add 1 mL of n-dodecane as internal standard. The filtered samples were analyzed by gas chromatography.[0180]The conversion, yield and selectivity were summarized in Table 3.[0181]Table 3[0182][0183]It can be seen that the conversion was above 90%and the selectivity can reach 100%at a mild hydrogenation condition with a temperature of 100-120and a hydrogen pressure of 40 bar under diluted condition.
84.9%
With hydrogen In water at 250℃; Inert atmosphere; Autoclave;
1
Examples 1 to 10 and Comparative Examples 1 and 2A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass of each of the catalysts A to J and catalysts L and M respectively produced in Catalyst Production Examples 1 to 10 and Comparative Catalyst Production Examples 1 and 2 (on the basis of the raw amide compound). An inside of the autoclave was purged with nitrogen, and then hydrogen was introduced thereinto until an inside pressure of the autoclave was increased to 1.5 MPaG. Thereafter, while maintaining the inside pressure of the autoclave at 1.5 MPaG, hydrogen was introduced into the reaction system at a rate of 40 L/h (1.35 mol/h per 1 mol of the raw amide compound). Next, the obtained reaction mixture was heated to 250° C. at which the hydrogen reduction thereof was carried out. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom. Then, the thus separated reaction solution was analyzed by gas chromatography to measure the content of the raw amide therein and the composition thereof with the passage of time, thereby calculating a reaction rate at the time at which 6 hours elapsed from initiation of the reaction and an amount (mass %) of N,N-dimethyl lauryl amine produced when the amount of the raw amide was reduced to 5%. The results are shown in Table 1. Meanwhile, the catalysts L and M both suffered from considerable deterioration in activity owing to occurrence of sintering during the reaction, so that the reaction was stopped in mid course and, therefore, failed to be completed.
With copper manganese at 270℃; Hydrogenation;
99 %Chromat.
With hydrogen In 1,2-dimethoxyethane at 130℃; for 1h; Autoclave;
2.3. Catalytic evaluation
General procedure: The Catalytic hydrogenation of amides N,N-dimethyldodecanamide1a (99 %, Solvay), N,N-dimethylhexylamide 1b, azepan-2-one 1c,dodecanamide 1d, benzamide 1e, isophthalamide 1f, and decanediamide1 g (99 %, J&K Chemical) was performed in a 30 mLstainless-steel autoclave. Typically, 0.5 mmol of the amide was firstdiluted in 5 mL of dimethoxy ethane (DME) (99 %, J&K Chemical)solvent. The obtained reaction mixture was charged into the reactor,followed by the addition of 0.1 g of catalyst. Then, the autoclave wassealed, purged several times with hydrogen and finally, pressurized upto the desired H2 pressure at room temperature. The charged reactor wasplaced in a preheated aluminum block at the desired temperature andtime under constant stirring 600 rpm. When the reaction was completed,the reactor was quenched with ice water. After cooling the reactor toroom temperature and depressurization to atmospheric pressure, ndodecane(99 %, J&K Chemical) was added to the reaction mixture as an external standard. The liquid reaction mixture was filtered and analyzedby GC-FID and GC-MS.
1000L reaction vessel was added100.00 kg (469.5 mol) of dodecyldimethylamine,62.40 kg (493.0 mol) of benzyl chloride and 300.00 kg of acetone,Stir at 40 C for 3 h.Then cool down to 0 C.After the solids are precipitated,filter,Dryed 145.88 kg of white solid,The total yield was 92.5%.The purity of dodecyldimethylbenzylammonium chloride was 99.6%.
91.5%
In acetone; at 50℃; for 5.0h;Autoclave; Large scale;
Add 100.00kg (469.5mol) to the 1000L reactorDodecyldimethylamine, 62.40 kg (493.0 mol) of benzyl chloride and 400.00 kg of acetone were stirred at 50 C for 5 h. Then cool down to 0 C. After the solid was precipitated, it was filtered and dried to give 145.88 kg of a white solid.The total yield was 91.5%.The purity of dodecyldimethylbenzylammonium chloride was 99.5%.
80%
In water; at 60 - 65℃; for 0.3h;
General procedure: Alkylation of tertiary amines 6a,c-h in water (general procedure). A mixture of amine 6a,c-h (6 mmol) and alkylchloride (6 mmol) in water (2-3 mL) was stirred at 60-95 for 0.3-4 h and then evaporated in vacuo. The residue was purified by column chromatography on silica gel in a CHCl3-MeOH (10 : 1) system or by recrystallization. The reaction conditions in each particular case, yields, and physicochemical parameters of quaternary ammonium compounds 1a-g, 2a-c, and 5a-c are presentedin Table 3. The data of the 1H NMR spectra are given in Table 5.
at 60℃; for 1.5h;Large scale;
78 kg Dodecyl dimethyl tertiary amine placed in a jacketed reactor, 46.5 kg of benzyl chloride was placed in the tank,After the reaction was heated to 60 C,Benzyl chloride was added at a uniform rate for 1 hour with stirring,To benzyl chloride all added, continue to stir the reaction 0.5h, after the end of the reaction,Cooling and filtering to obtain dodecyldimethylbenzylammonium chloride
In ethyl acetate; at 85℃; for 10.0h;
The dodecyl dimethyl tertiary amine, benzyl chloride and ethyl acetate were measured by the formula, respectively, and the molar mass ratio of the dodecyldimethyl tertiary amine and benzyl chloride was 1: 1; (2) Ethyl acetate into the 300L glass-lined reactor, the dodecyl dimethyl tertiary amine and benzyl chloride were thrown into the high slot, open the reactor of the mixing device, at room temperature dodecyl dimethyl Amine and benzyl chloride in the same proportion into the reactor; (3) open the heating device, the reactor heated to 85 C, insulation reaction 10 hours; (4) open the circulating cooling water, the product cooled to room temperature, to the crystal completely precipitated; (5) to take out the precipitation of crystals, decompression pumping, the process of taking the acid ethyl acetate 3 times to wash the crystal, to retain the filter cake; (6) in the filter cake by adding ethyl acetate for recrystallization, the crystal at -1.5Mpa, 60 C under vacuum conditions to dry weightThat is high purity pharmaceutical grade benzalkonium chloride monomer.
With aluminum (III) chloride; In ethyl acetate; at 60℃; for 4.0h;
(1) 2 moles of dodecyldimethylamine, 2 mol of aluminum chloride, 2.4 mol of benzyl chloride, 100 mL of ethyl acetate, respectively,(2) dissolving the dodecyldimethyl tertiary amine and aluminum chloride in ethyl acetate to obtain a mixed system, placing the mixed system in a hydrothermal boiler, raising the temperature of the mixed system to 60 C,(3) The benzyl chloride was added dropwise to the mixed system of step (2) under conditions of constant stirring, and the dropping rate was 30 to 40 drops / min. After completion of the dropwise addition, the stirring was stopped and allowed to stand for 4 hours to obtain Benzalkonium chloride monomer;(4) The mixed system of step (3) was suction filtered, washed three times, and recrystallized from ethyl acetate to give benzalkonium chloride.
2.1.2. Synthesis of compounds 2-4
General procedure: A mixture of 1-bromoalkane (0.10 mol) and dimethylamine (33%aqueous solution, 0.50 mol, 5 equiv) in ethanol (40 mL) was added to a dried 100 mL 2-necked flask. The solution was heated at 80 °C for 24 h. After the reaction mixture was cooled to room temperature, the solvent was removed under vacuum, and the residue was poured into the saturated sodium bicarbonate solution (60 mL). The mixture was extracted with ethyl acetate, and the extract phase was dried with anhydrous magnesium sulfate. The solvent was removed by distillation under reduced pressure and the solid residue was purified by distillation to give compounds 2-4 as colorless oily products. N,N-dimethyldodecylamine (2, 20.15 g, 93.62% yield based on 1-bromododecane). 1H NMR (400 MHz, CDCl3, TMS) δ ppm: 0.86-0.90(t, J = 8.0 Hz, 3H), 1.28-1.26 (d, J = 8.0 Hz, 18H), 1.47 (s, 2H), 2.23-2.30 (m, 8H); IR (KBr) cm-1: 2925, 2854, 1464, 721.
84%
With sodium hydroxide In water; benzene at 20 - 25℃; for 20h;
Tertiary amines 6a,c-e and 6f-h (general procedure).
General procedure: A mixture of a 38% aqueous solution of dimethylamine (80 mmol) or N-butyl-N-methylamine4 (60 mL), alkylating agent (40 mmol), and a 50% aqueous solution of NaOH (44 mmol) was stirred at 20-115 °C under atmospheric pressure or kept in a sealed ampule for 5-45 h. The reaction mixture was diluted with benzene (15 mL) and water (10 mL). The organic layer was separated, washed with water (3×10 mL), dried with Na2SO4, and evaporated in vacuo. The residue was distilled. The reaction conditions in each particular case, yields, and physicochemical parameters of tertiary amines 6a-h are presented in Table 1. The data of the 1H NMR spectra are given in Table 2.
With ethanol
In ethanol
In methanol
20.15 g
In ethanol; water for 24h; Reflux;
2.2.2. Compounds 2-4
General procedure: A mixture of 1-bromoalkane (0.1 mol) and dimethylamine (33%aqueous solution, 0.5 mol, 5 equiv) in ethanol (40 mL) was placed in adried 3-necked flask (150mL). After stirring for 24 h at reflux, the reactionmixture was cooled to room temperature. The solvent was removedunder vacuum, and the residue was poured into the saturatedsodium bicarbonate solution (60 mL). The mixture was extracted withethyl acetate, and the extract phase was washed with water, thendried over anhydrous magnesium sulfate. The solvent was removed toand the residue was purified by distillation to give compounds 2-4 ascolorless oily products.N,N-Dimethyldodecylamine (2, 20.15 g, 98.96% content for GC,93.62% yield based on 1-bromododecane). 1H NMR (400 MHz, CDCl3,TMS) δ ppm: 0.86-0.90 (t, J = 8.0 Hz, 3H), 1.26-1.28 (d, J = 8.0 Hz,18H), 1.47 (s, 2H), 2.23-2.30 (m, 8H); IR (KBr) cm-1: 2925, 2854,1464, 721; GC-MS (m/z: 213.3 g mol-1), 58.2 (M-C11H23).
Synthesis of quaternary ammonium compounds 1a-g, 2a-c, and 5a-c.
General procedure: Alkylation of tertiary amines 6a,c-h in water (general procedure). A mixture of amine 6a,c-h (6 mmol) and alkylchloride (6 mmol) in water (2-3 mL) was stirred at 60-95 for 0.3-4 h and then evaporated in vacuo. The residue was purified by column chromatography on silica gel in a CHCl3-MeOH (10 : 1) system or by recrystallization. The reaction conditions in each particular case, yields, and physicochemical parameters of quaternary ammonium compounds 1a-g, 2a-c, and 5a-c are presentedin Table 3. The data of the 1H NMR spectra are given in Table 5.
With sodium hydroxide In acetonitrile at 90℃; for 8h;
1 Example 1:
5.2g of 1,2-dibromoethane and 30mL of acetonitrile were added to the flask, and it heated at 90 degreeC. After fully stirred, the acetonitrile solution containing 4.0 g of N,N-dimethyldodecyl tertiary amine was slowly added through a constant pressure dropping funnel, and the pH of the system was controlled by sodium hydroxide at 10.0, and the reaction was continued at this temperature for 8 hours. . The solvent was removed to obtain intermediate M in a yield of 89%. Weigh 3.9g of the intermediate M and 0.6g of sodium selenide dissolved in 20mL of deionized water, heat to 60°C and stir for 12 hours. After removing the solvent, recrystallization with ether can obtain the gemini surfactant 12-2-Se-2-12 with a single selenium atom in the spacer, and the yield reaches 90%
A mixture of N, N-dimethyldodecylamine (50 mmol) and 1, 3-propanesultone (52mmol) in ethanol (20 mL)was stirred at roomtemperaturefor 24 h. On completion, this reaction system was placed in anice-water bath and cooled to 0-5 C, the resulting precipitate was filtered,washed with diethyl ether, and dried at 65 C under a vacuumfor 8 h to afford precursor zwitterionic salt (1) in a yield of 95%.
In ethyl acetate; at 20℃;
General procedure: The laboratory synthesis of sulfobetaines that belong to thegroup of N-alkyl-N,N-dimethyl-3-ammonio-1-propanesulfonateand N-alkyl-N,N-dimethyl-4-ammonio-1-butanesulfonate(Fig. 1) was carried out by the reaction of 1,3-propanesultone or 1,4-butanesultone with correspondingN,N-dimethylalkylamine in ethyl acetate at room temperature.The resulting crystalline products were separatedfrom the reaction mixture by filtration and further purifiedby recrystallization. The structure of the obtained compoundswas confirmed by spectroscopic methods and elementalanalysis. All surfactants synthesized are listed inTable 1.
With hydrogen; dimethyl amine In water at 250℃; Inert atmosphere; Autoclave;
12
Example 12 The procedure was conducted in the same manner as in Example 2. After confirming that the amount of the raw amide contained in the reaction product as measured by gas chromatography was reduced to 0.5% by mass, successively, while maintaining the same reaction temperature and pressure as well as the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 3 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated reaction solution was analyzed by gas chromatography. The results are shown in Table 2. Meanwhile, as a result of analyzing the reaction product by gas chromatography, it was confirmed that the content of the raw amide therein was reduced below the lower detection limit.
With sodium dimethylaminoborohydride In tetrahydrofuran at 66℃; for 5.5h; Yield given. Yields of byproduct given. Title compound not separated from byproducts;
In methanol; at 65 - 142℃;Conversion of starting material;
A 1-liter, creased, 4-necked round bottom Pyrex flask equipped with mechanical stirrer, 250-milliliter (ml) addition funnel, temperature probe, heating mantle, and water-cooled total reflux condenser was used. The flask was initially charged with 200 grams (1.08 mole) of ADMA-10 (decyldimethylamine, available from Albemarle Corporation, Baton Rouge, LA), and 239 grams (1.08 mole) decyl bromide was placed in the addition funnel. The stirrer was turned on and the reactor was heated to 65C. The decyl bromide was added dropwise to the ADMA-10 as the temperature of the reactor was allowed to rise from 65C to 142C. The addition funnel was then charged with 110 grams of methanol, and the methanol was added dropwise to the solution as the temperature of the reactor was allowed to fall to 90C. After the entire volume of the methanol was added to the reaction mixture, the heat and stirring were ceased and the intermediate quaternary ammonium (quat-Br) solution was allowed to cool.
1
Comparative Example 1A catalyst was similarly reduced as in Example 1, except that a reduction temperature of the catalyst was 200° C. and a reduction time was 90 minutes.After the reduction of the catalyst, 750 g of lauryl alcohol (Kalcol 20, manufactured by Kao Corporation) was charged in the buffer tank 2. While supplying a hydrogen gas to the tube reactor 1 at a flow rate of 16.5 L/hr based on a standard state volume, a reaction mixture was circulated at 5.9 L/hr between the buffer tank 2 and the tube reactor 1. After an inside temperature of the tube reactor 1 reached 220° C., dimethylamine was supplied at the temperature to start the reaction. A supplying rate of dimethylamine was controlled according to progress of the reaction, and a reaction time-averaged rate of 65 g/hr. A reaction mixture was analyzed over time by gas chromatography. When an amount of unreacted lauryl alcohol was reduced to 1% (6.7 hours after the start of the reaction), supply of dimethylamine was stopped to finish the reaction. A sample of the reaction mixture at the end of the reaction was collected to determine quantities of ingredients by the area percentage method of gas chromatograph. A reactivity per weight of catalytically active substance, α, was similarly determined as in Example 1. Results are shown in Table 2.
1: 1.9 % Chromat.
2: 97.0 % Chromat.
at 199.9℃; for 5h;
1: 87.4 - 89.7 %Chromat.
2: 7.8 - 9.5 %Chromat.
at 220℃; for 5.9 - 6.2h;
1: 89.9 - 90.4 %Chromat.
2: 7.4 - 8.2 %Chromat.
at 220℃; for 3.8h;
With hydrogen at 220℃; for 1.6 - 3h;
1; 2; 1
The film type catalyst A obtained in Manufacture Example 1 was loaded on to the inside of the tube-reactor 1 having an inner diameter of 29.5 mm. The loaded portion of the film type catalyst had a length of 390 mm, and a volume of 0.267 L to form plural flow paths having a cross-sectional area of around 0.1 cm2 that communicated in the axial direction of the reactor 1 by the film type catalyst. 1.0 kg of lauryl alcohol (Kalcol 20, manufactured by KAO CORPORATION) was charged in the raw material tank 7 and, while feeding hydrogen gas in a flow volume of 20 L/Hr in terms of the volume in the standard state, the liquid superficial velocity of the tube-reactor 1 was set at 0.30 cm/s.The raw material was fed continuously from the raw material tank 7 to the reactor 1 and, after raising the inside temperature of the reactor 1 up to 220° C., the reaction was begun by feeding dimethylamine. The unreacted raw materials and a mixture of the reaction products flowing continuously from the outlet of the reactor 1 were collected into the product tank 8. A cycle was repeated, in which the mixture collected into the product tank 8 was fed again continuously from the raw material tank 7 to reactor 1 by the similar operation and those subjected to the reaction in the reactor were collected into the product tank 8.After 3 hours from the beginning of the reaction, the feed of the dimethylamine was stopped, and the whole volume of the liquid within the product tank 8 and reactor 1 was drawn. The liquid was analyzed with gas chromatograph. The result of quantification by the area percentage method gave 12.3% of unreacted lauryl alcohol, 82.3% of generated DM type, and 3.8% of M2 type being side produced tertiary amine. N,N,N-tridodecylamine was not detected; The internal temperature of the reactor 1 was raised up to 220° C. in the same operation as in Example 1 except for setting the liquid superficial velocity of the tube-reactor at 0.20 cm/s, and then the reaction was begun by feeding dimethylamine. The feed volume of the dimethylamine was adjusted in accordance with the progress of the reaction, and 86 g/Hr in the reaction time average.After 3 hours from the beginning of the reaction, the feed of the dimethylamine was stopped, and the whole volume of the liquid within the product tank 8 and reactor 1 was drawn. The liquid was analyzed with gas chromatograph as was the case with Example 1. The result gave 12.6% of unreacted lauryl alcohol, 80.1% of generated DM type, and 5.0% of M2 type being side produced tertiary amine; The film type catalyst A obtained in Manufacture Example 1 was loaded onto the inside of the tube-reactor 1 having an inner diameter of 28.5 mm. The loaded portion of the film type catalyst had a length of 800 mm, and a volume of 0.510 L to form plural flow paths having a cross-sectional area of around 0.1 cm2 that communicated in the axial direction of the reactor 1 by the film type catalyst. The internal temperature of the reactor 1 was raised up to 220° C. in the same operation as in Example 1 except for setting the liquid superficial velocity of the reactor 1 at 0.01 cm/s, and then the reaction was begun by feeding dimethylamine at 220° C. The feed volume of the dimethylamine was set at a constant value of 66 g/Hr. The liquid reacted and sent to the product tank 8 was drawn every 1 hour. The drawn liquid was analyzed with gas chromatograph. The result of quantification by the area percentage method (result of one-pass analysis) gave 14.5% of unreacted lauryl alcohol, 73.2% of generated DM type, and 10.3% of M2 type being side produced tertiary amine. N,N,N-tridodecylamine was not detected.The results of Examples 1-4 and Comparative Example 1 are shown collectively in Table 1.
With hydrogen at 220℃; for 1h;
3; 4
The film type catalyst B obtained in Manufacture Example 2 was loaded onto the inside of the reactor 1 having an inner diameter of 101 mm. The loaded portion of the film type catalyst had a length of 2160 mm, and a volume of 17.4 L to form plural flow paths having a cross-sectional area of around 0.1 cm2 that communicated in the axial direction of the reactor 1 by the film type catalyst. 46.1 kg of lauryl alcohol (Kalcol 20, manufactured by KAO CORPORATION) was charged in the buffering tank 2 and, while feeding hydrogen gas in a flow volume of 922 L/Hr in terms of the volume in the standard state, the liquid was circulated between the buffering tank 2 and reactor 1, and the liquid superficial velocity of the tube-reactor 1 was set at 2.40 cm/s. After raising the temperature within the reactor 1 up to 220° C., the reaction was begun by feeding dimethylamine at 220° C. The feed volume of the dimethylamine was adjusted in accordance with the progress of the reaction. After 1 hour from the beginning of the reaction, the feed of the dimethylamine was stopped, and the whole volume of the liquid within the buffering tank 2 and reactor 1 was drawn. The liquid was analyzed with gas chromatograph. The result of quantification by the area percentage method gave 15.3% of unreacted lauryl alcohol, 78.6% of generated DM type, and 3.7% of M2 type being side produced tertiary amine. N,N,N-tridodecylamine was not detected; The internal temperature of the reactor 1 was raised up to 220° C. in the same operation as in Example 3 except for setting the liquid superficial velocity of the reactor 1 at 0.80 cm/s, and then the reaction was begun by feeding dimethylamine. The feed volume of the dimethylamine was adjusted in accordance with the progress of the reaction. After 1 hour from the beginning of the reaction, the feed of the dimethylamine was stopped, and the whole volume of the liquid within the buffering tank 2 and reactor 1 was drawn. The liquid was analyzed with gas chromatograph in the same way as in Example 3. The result gave 13.9% of unreacted lauryl alcohol, 80.2% of generated DM type, and 4.4% of M2 type being side produced tertiary amine.
Stage #1: 1-dodecyl alcohol at 220℃;
Stage #2: dimethyl amine at 211 - 215℃;
Stage #3: With hydrogen at 160℃;
2
In this example, 770 g mixture containing 72.7% N- dodecyl-N,N-dimethylamine and 26.3% lauryl alcohol (KALCOL 20 manufactured by Kao Corporation) as starting alcohol was introduced into vessel 14, then the atmosphere in the vessel 14 was replaced by a nitrogen ga.s , and the mixture was heated to 60°C. Then, each conduit and the reaction towers 5 to 7 were heated to 60°C, and then the supply of a nitrogen gas into the reaction tower 5 and the supply of a hydrogen gas into the reaction tower 7 were initiated. Then, pump 8 was actuated to initiate supply of the starting alcohol into the reaction tower 7. The starting alcohol was passed through the reaction towers 5 and 6 in this order, and it was confirmed that the starting alcohol recovered in each reaction tower was circulating. Then, the solution in the reaction tower 5 and in the vessel 14 was heated to a temperature of 220°C, and the reaction tower 7 was heated to 1600C, and then dimethylamine was fed to the reaction tower 6 (temperature of which was not controlled) to initiate the reaction. Simultaneously, a nitrogen gas was fed to the solution in the vessel 14 to initiate bubbling.The flow rate of the circulating solution was 4.0 L/hr, the feed rate of a nitrogen gas into the reaction tower 5 was 70 NL/hr, and the feed rate of a hydrogen gas into the reaction tower 7 was 90 NL/hr. The feed rate of a nitrogen gas into the solution in the vessel 14 was 70 NL/hr.The sample was collected with time and analyzed with gas chromatography and quantified by the area percentage method, and the solution was circulated and reacted until the unreacted lauryl alcohol as the starting material was reduced to 3.3%. Thereafter, the supply of the gas and liquid was stopped, and the atmosphere was replaced by a nitrogen gas, and the whole solution was removed. The amount of dimethylamine fed was regulated in the range of 12 to 22 g/hr (17 g/hr on average during the reaction) depending on the progress of the reaction. The temperature of the reaction tower 6 was 211 to 215°C. As a result of analysis by gas chromatography, it was revealed that when the increased amount of N-dodecyl-N,N-dimethylamine was 11.0%, the increased amount of the tertiary amine side product N,N-didodecyl-N-methylaτnine was 0.3%, and the tertiary amine side product N,N,N-tridodecylamine was not detected (that is, no increase thereof) . When the increased amount of N-dodecyl-N,N-dimethylamine was 20.9%, the increased amount of the tertiary amine side product N, N- didodecyl-N-methylamine was 1.0%, and the tertiary amine side product N, N, N-tridodecylamine was not detected (that is, no increase thereof) .
With hydrogen at 220℃;
Using the circulating fixed-bed reactor shown in Fig. 3, N-dodecyl-N,N-dimethylamine was produced from lauryl alcohol and dimethylamine as the starting materials.The reaction tower 16 in Fig. 3 is a vertical tubular fixed-bed reactor having an inner diameter of 29.5 mm and was loaded with 270 cc of the film-type catalyst obtained in Production Example 3 as a dehydrogenation catalyst after subjected to reduction treatment (there was no catalyst in a buffer tank 17). 1000 g mixture containing 72.0% N- dodecyl-N, N-dimethylamine and 27.0% lauryl alcohol (KALCOL 20 manufactured by Kao Corporation) as starting alcohol was introduced into the buffer tank 17, then the atmosphere in the tank 17 was replaced by a nitrogen gas, and the solution was heated to 60°C. While a hydrogen gas was fed at a flow rate of 20 NL/hr, circulation of the solution was initiated at a flow rate of 7.5 L/hr between the buffer tank 17 and the reaction tower 16.After the reaction tower 16 was heated to a temperature of 220°C, dimethylamine was fed to the reaction tower 16 to initiate the reaction at 220°C. The sample was collected with time and analyzed by gas chromatography and quantified by the area percentage method, and the solution was reacted under circulation until the unreacted lauryl alcohol as the starting material was reduced to 1.9%. Thereafter, the supply of dimethylamine was stopped, and the atmosphere was replaced by a nitrogen gas, and the whole solution was removed. The amount of dimethylamine fed was regulated in the range of 60 to 110 g/hr (85 g/hr on average during the reaction) depending on the progress of the reaction. As a result of analysis by gas chromatography, it was revealed that when the increased amount of N-dodecyl-N,N-dimethylamine was 10.2%, the increased amount of the tertiary amine side product N,N-didodecyl-N- methylamine was 1.4%, and the tertiary amine side product N,N,N-tridodecylamine was not detected (that is, no increase thereof). When the increased amount of N-dodecyl-N,N- dimethylamine was 17.2%, the increased amount of the tertiary amine side product N,N-didodecyl-N-methylamine was 4.3%, and the tertiary amine side product N, N, N-tridodecylamine was not detected (that is, no increase .thereof) .The reaction conditions and the results in Example 2 and Comparative Example are collectively shown in Table 1.
1: 78.9 %Chromat.
2: 17.2 %Chromat.
With hydrogen at 220℃; for 3.3h;
1
Comparative Example 1; In the same way as in Example 1, the film catalyst A prepared in Preparation Example 1 was loaded in the inside of the reactor 1 and reduced by the same operation as in the Example 1.600 g of lauryl alcohol (Kao Corporation, Kalcol 2098) was fed in the buffer tank 2. With supplying a hydrogen gas at a flow rate of 16.5 L/Hr in terms of volume under standard conditions, the alcohol was circulated at 5.92 L/Hr between the buffer tank 2 and the reactor 1. The inside temperature of the reactor 1 was increased to 185° C., and dimethylamine was supplied to the reactor 1. The inside temperature of the reactor 1 was further elevated to 220° C. to start the reaction. Dimethylamine was supplied in a feeding amount, adjusted according to progress of the reaction, of 42 g/Hr on the average in view of the reaction time. After 3.3 hours from the start of the reaction, the feeding of dimethylamine was stopped, and the whole system was cooled. All the liquid in the buffer tank 2 and the reactor 1 was collected. The collected liquid was analyzed by gas chromatography to quantify by the area percentage method. Results showed that: 0.5% of unreacted lauryl alcohol, 78.9% of N-dodecyl-N,N-dimethylamine, and 17.2% of N,N-didodecyl-N-methylamine, which were generated. N,N,N-tridodecylamine was not detected.
With tetra-(n-butyl)ammonium iodide; potassium carbonate In 1,4-dioxane; water; acetonitrile at 60℃; for 24h;
4.5.1.12 Synthesis of Dimethyldodecylamine (433)
General procedure: 433nEntry 1: According to general procedure IV (chapter 2.2.1) 1-dodecanol(215 ilL, 186 mg, 1.00 mmol, 1.0 equiv), FPyr (19.7 ilL, 20.4 mg, 0.20 mmol, 20 mol%),(0.5 mL, 2 M) and benzoyl chloride (141 ilL, 170 mg, 1.20 mmol, 1.2 equiv) were combinedambient temperature and allowed to react at 80 °C for 2 h. Afterwards to the reaction solutionadded MeCN (1.5 mL, dioxane/MeCN 1:3, 0.5 M), K2C03 (320 mg, 2.30 mmol, 2.3 equiv), TBAI0.10 mmol, 10 mol%) and an 40% aqueous solution of dimethylamine in water (250 ilL,2.0 equiv) and the resulting suspension was stirred for 24 h at 60 °C. Then chromatographicpurification of the crude material (330 mg) on silica gel (mass of crude material/Si02Et20/NEt3/nPen 20:5:75 delivered the amine 433as a pale yellow oil (157 mg, 0.736 mmol,
dimethyl dodecyl 3-hydroxypropyl ammonium bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
88%
In acetonitrile at 75℃; for 20h; Inert atmosphere;
4 Example 4
n a 250 mL three-necked flask, 21.34 g of dodecyldimethyl-tertiary amine and 15.14 g of 3-bromopropan-1-ol were added and added.60 mL of acetonitrile was used as a solvent and reacted under inert gas atmosphere at 75°C for 20 hours. After the reaction is complete, the solvent is removed by rotation to obtain29.6 g of a bright yellow oily viscous liquid, designated C18NPBr, with a yield of 84%. Subsequently, add 17.6 in a 150 mL round bottom flaskGrams of C12NOBr and 10.1 g of acesulfame Potassium, dissolved in absolute ethanol, and the solution was thoroughly stirred at 60 °C for 24 cycles. hour. The white powder is a crude product of a water-soluble surfactant, which is removed by suction filtration. The fully reacted acesulfame potassium and ion exchanged salt to ethanol phase were clear and the solvent was rotavaped to give a white solid. will The white solid was dried in a vacuum oven at 60°C for 12 hours to obtain 19.1 g of surfactant NOAK powder in a yield of88%.
2.2. Improved solvent-free synthesis of GS1
To synthesis of GS1, a mixture of 1,3-dichloro-2-propanol (5 mmol)and NNDDA (10 mmol) in a round bottomed flask was magnetically stirred under solvent-free conditions at 70 °C for 8 h. Then, the rawmaterialswerewashedwithdiethyl ether (2 × 50 mL) and acetone and thegiven white solid was dried in vacuum to give 96% yield of GS1. Thestructure of the GS1 was confirmed by FT-IR, 1H NMR, melting point,and CHN analysis, in accordance with the same reported literaturedata for GS1 prepared by previous procedures [24-28].
73%
In propan-1-ol for 24h; Heating;
With sodium iodide In methanol at 70℃; for 48h;
3 Example 3:
Dissolve 1,3-dichloro-2-propanol and N,N-dimethyldodecyl tertiary amine in a molar ratio of 1.0:2.8 in methanol, add catalyst sodium iodide, and raise the temperature to 70, 48h reaction,Most of the solvent is removed by distillation under reduced pressure, and suction filtration is added with petroleum ether to obtain a white intermediate product;Dissolve the obtained intermediate product with acryloyl chloride and neutralizing agent sodium hydroxide in a molar ratio of 1.0:1.3:1.3 in dichloromethane and react at 40°C for 20h,Wash with dilute hydrochloric acid, saturated sodium bicarbonate solution, saturated sodium chloride, and deionized water in this order,Anhydrous sodium sulfate was dried, filtered, and the solvent was distilled off under reduced pressure to obtain the monomer AEG12 of quaternary ammonium acrylate.
diethyl-ether-α,ω-bis(dimethyldodecylammonium chloride)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
67%
In propan-1-ol for 24h; Heating;
With sodium carbonate In water; isopropyl alcohol at 60 - 95℃; for 8h;
3; 6 example 3
Weigh dodecyl dimethyltertiary amine 42.6g (0.2mol), deionized water 58g, add 0.8g of sodium carbonate solids to the four-neck bottle, turn on the agitation and heat. Weigh 15.1g (0.105mol) of dichloroethyl ether put into the dropping funnel, when the temperature reaches at 60 ° C, it starts to add drops, control the dropping time 20min. Wait until the dichloroethyl ether is added, the reaction temperature is controlled at 95°C, and the reaction time is 8 h, can be obtained product diethyl ether-a, ω- Di-dodecyl dimethyl ammonium chloride. Chemical analysis (water/chloroform two-phase titration, bromophenol blue as indicator, titrated with sodium tetraphenylborate standard solution), and then calculated, the reaction yield was 82.02wt%. the liquid product obtained in the above step is rotary evaporated to remove the solvent, wash 5 times with diethyl ether to remove excess reactant dichloroethyl ether, and then washed 5 times with acetone to remove excess reactant tertiary amine and solvent. Drying in vacuum for 48 h and then obtained a cream solid. Chemical analysis (water/chloroform two-phase titration, bromophenol blue as indicator, titrated with sodium tetraphenylborate standard solution), and then calculated, the purity after separation and purification is 96.76wt%.
With 1-benzyl-1-azonia-4-azabicyclo[2.2.2]octane tetrahydroborate In <i>tert</i>-butyl alcohol at 20℃; for 1h;
74%
With formic acid In ethanol for 8h; Reflux;
1 Embodiment 1: dodecyldimethylamine preparation
With mechanical stirring in 250 ml four-mouth bottle in, adding 18.5 g ten diamidogen and 70 ml anhydrous ethanol, to control the temperature 20 °C following entry into the 20.9 g 88% formic acid and 24.3 g 37% formaldehyde, balloon for closed reaction system, heating to reflux the reaction 8 hours, cooling sampling, TLC detection reaction is complete. To the reaction solution by adding 30% liquid caustic soda and to pH value in 10, the toluene is added to the extraction, washing of the toluene after the merger, desolvation, distilling and getting the colorless transparent liquid 15.6 g, yield 74%, content ≥ 95.0%.
With dodecyldimethyl ammonium chloride In ethanol at 80℃; for 8h;
92.87%
With hydrogenchloride In isopropyl alcohol at 50 - 90℃; for 12h;
4.1
1) The weighed 0.021mol dodecyl dimethyl amine containing 10mL of isopropanol was added 100mL three-necked flask was heated to 50 , then hydrochloric acid solution was added dropwise thereto 4.0mL2.5mol / L of under 750r / min and stir until uniform.Gradually dropping 0.01mol epichlorohydrin into the system within 30 minutes, dropping while taking temperature program, beginning when the temperature dropped to 50 , heated to 90 when the addition was complete, the addition was complete start time, reaction 12h, heating was stopped to give the crude product, the crude product was 85 , 0.09MPa under reduced pressure to remove the solvent by rotary evaporation, then at 60 was dissolved in acetone and recrystallized at room temperature, suction filtered, reconstituted, after repeated three times, and dried, to give a quaternary ammonium salt of hydroxypropyl Gemini; 92.87% yield.
87.9%
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In water; isopropyl alcohol for 0.5h;
Stage #2: epichlorohydrin In water; isopropyl alcohol at 50 - 130℃; for 12h;
1.1
Referring to Figure 3, 0.02 mol of dodecyldimethyl tertiary amine, weighed, was added 10 mL of isopropanol, heated to 50deg C, and then added dropwise thereto 4.0 mL of 2.5 mol / L hydrochloric acid solution, stirred at 450 r / min until homogeneous. 30 minutes gradually to the system by adding 0.01mol of epichlorohydrin, dropping at the same time take the program temperature, The temperature at the start of the dropping was 50 ° C, the temperature was raised to 130 ° C at the time of completion of the dropwise addition, the start of the dropping was started, the reaction was continued for 12 hours, The heating was stopped to obtain a crude product, and the crude product was distilled under reduced pressure at 85 ° C and 0.09 MPa to remove the solvent, And then dissolved in acetone at 60 ° C, and recrystallized at room temperature, suction filtration, re-dissolved, repeated three times, Dried to give the hydroxypropylgis dibutyl quaternary ammonium salt (designated as 12-3 (OH) -12); the yield was 87.9%.
39%
In butan-1-ol at 70℃; for 8h;
2.2. Synthesis and characterization of 1,3-bis(dodecyldimethylammonio)-2-hydroxypropane dichloride (GS)
The GS was prepared according to the previously reported methods[34-37] by reaction of (5 mmol) epichlorohydrin and N,N-dimethyldodecylamine (10 mmol) in n-butanol at reflux conditionsfor 8 h [37]. After the completion of the reaction, the solvent was evaporated to give a 39% white solid powder of GS. The structure of GS was assigned by FT-IR, 1H NMR, melting point, and CHN analysis, although the given results were in accordance with some of the previously reported literature data for GS [36]
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In water for 0.5h;
Stage #2: epichlorohydrin In water at 60℃; for 12h;
Stage #1: N,N-dimethylaminododecane; epichlorohydrin In ethanol; water at 50℃; for 3h; Large scale;
Stage #2: With hydrogenchloride In ethanol; water at 70℃; for 3h; Large scale;
Preparation of double-dodecyl dimethyl hydroxypropyl double quaternary ammonium chloride bactericide
The first step lauryl tertiary amine 50 kg,Ethanol 38 kg,71 kilograms of water into the vacuum reactor,Stirred and warmed to 50 ° C,Then add 23 kg of epichlorohydrin,There will be a heat generated at this time,Control the reactor temperature of raw materials 50 ,Then stirred for 3 hours The second stepIn the reactor was added dodecyl tertiary amine 50 kg,Hydrochloric acid 17 kg,71 kilograms of water,The temperature of the kettle material was controlled at 70 ,The reaction was stirred for 3 hours; third stepWith hydrochloric acid mixture of the reaction kettle to adjust the PH value to 8 ± 2,The reaction was stirred for a further 0.5 hour,Namely made of the double-dodecyl dimethyl hydroxypropyl double quaternary ammonium bactericide
N-(3-chloro-2-hydroxypropyl)-N,N-dimethyldodecan-1-aminium chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
76%
at 60℃; for 2h;
Preparation of YB
YB was synthesized from N,N-dimethyl-1-dodecylamine and EH. EH solution (219mL, 2.79mol) was added dropwise to a 300 mL (1.11mol) solution of N,N-dimethyl-1-dodecylamine. The mixture was stirred at 60 °C for 2 h to obtain a highly viscous solution, and the residual EH was removed by a procedure using vacuum-rotary evaporation. After the product was cooled to room temperature, it was dissolved in acetone(500 mL). Crystals began to separate in a few minutes. After the mixture was stored for 8 h at 25 °C, it was filtered. The crystal-like products were washed with diethyl ether and then dried at 60°C under vacuum for 24 h. The product obtained was labeled as YB. The yield was 76% which approximated to the yield of 77% in the reference. The reaction involved in this process is shown in Fig. 1. Results of its analysis are given below: Elemental analysis (YB, C17H37Cl2NO). Measured (%): N 4.14%, C59.73%, H 10.86%; calculated (%): N 4.09%, C 59.65%, H 10.82%.YB: 1H nuclear magnetic resonance spectrometer (1H NMR) (D2O, 300 MHz): δ 0.75 (t, 3H, J = 3.75), 1.16 (q, 18H, J = 8.2), 1.57 (q, 2H,J = 7.8), 3.20 (s, 6H), 3.45 (t, 2H, J = 4.8), 4.15 (d, 2H, J = 2.4), 6.18(d, 2H, J = 8.4), 6.29 (q, 1H, J=2.8).
With dodecyldimethyl ammonium chloride In ethanol at 50℃;
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In diethyl ether at 25℃; for 2h;
Stage #2: epichlorohydrin In acetone at 50 - 60℃; for 3h;
1.1
See FIG 1,1) to athree-necked flaskequipped withaNaClwas gradually added dropwise concentrated sulfuric acid (98% mass fraction), microHeat,gasgeneratingHC 1,HC 1and the generated gas through concentrated sulfuric acid (98% mass fraction) and dried, and then slowlySlow access equipped dodecyl dimethyl amine in ethersolution,25 ° C,under350r / min speed stirring constantly, to give a whiteThe precipitate is lauryl dimethyl aminehydrochloride,2 hafter completion of the reaction.Washed several times with ether to give pureDodecyl dimethyl aminehydrochloride,20 ° Cand dried under6h, standby.[0034]2) equipped with a25mLthree-necked flask of acetone was added7.497 g (0. 03 mol) dodecyl dimethyl amine saltSalt and0.3195 g (0. 0015 mol)dodecyl dimethyl amine at30° C, 400 r / min stirring for45min; increasesTemperature to50° C,at500r / min, the2.275 g (0. 03 mol) of epichlorohydrin(ECH)was added dropwise within60min completed,Aftercompletion of the reaction drops3hthe reaction was stopped; vacuum distillation removed excess solvent and reactant, multiple recrystallized from acetone to giveTo 3-chloro-2-hydroxypropyl - dimethyl dodecyl ammonium chloride, the yield can be as high as 94.5%.
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In ethanol; water at 25℃; for 0.5h;
Stage #2: epichlorohydrin In ethanol; water for 8h;
1 Example 1
The preparation method of the twelve carbon cationic asphalt emulsifier, the specific preparation steps are as follows: (1) Adding 0.1 mol of N,N-dimethyldodecylamine to a 250 mL single-necked flask at 25 ° C40 mL of ethanol, then 0.1 ml of hydrochloric acid was added dropwise, and the reaction was stirred for 0.5 h.Then, 0.1 mol of epichlorohydrin was continuously added dropwise, and the reaction was stirred for 8 hours, and the solvent was removed by rotary evaporation.Recrystallization from a mixed solution of ethanol and ethyl acetate (volume ratio 1:10), suction filtration,Vacuum drying to obtain intermediatesN-(3-chloro-2-hydroxy)propyl-N,N-dimethyldodecylammonium chloride
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In ethanol; water at 20℃; for 0.0833333h;
Stage #2: epichlorohydrin In ethanol; water at 55℃; for 6h;
1 Example 1:
First 100mmolDodecyl dimethyl tertiary amineIn ethanol,Next, 120 mmol of 37% hydrochloric acid was added to the round bottom flask.Stir at room temperature for 5 min to completely dissolve the hydrochloric acid into the solution. Then burn to200 mmol of epichlorohydrin was added to the bottle, and the temperature was raised to 55 ° C, and the reaction was carried out for 6.0 h.After the reaction is completed, the ethanol and the remaining epichlorohydrin are removed by rotary evaporation.Finally, a pale yellow viscous paste is obtained.And placed in a dry bottle for use, denoted as EPT-12, the nuclear magnetic spectrum shown in Figure 1.
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In water; diethylene glycol at 60℃; Inert atmosphere;
Stage #2: epichlorohydrin In water; diethylene glycol at 80℃; Inert atmosphere;
6; 9-11 Example 6. N1-dodecyl-2-hydroxy-N1,N1,N3,N3,N3-pentamethylpropane-1,3-diaminium chloride (1:2) in diethylene glycol
43.10 g of dimethylaurylamine (N,N-dimethyldodecylamine, 1.00 mol) was charged in a 500 mL flask. 40.00 g of diethylene glycol and 10.00 g of deionized water were charged in a 500 mL round bottom flask, mixed, and refluxed for 10 minutes under nitrogen blanket followed by dropwise addition of 19.46 g of 31-37% hydrochloric acid solution (0.98 mol) in the reaction with an addition funnel. Diethylene glycol was selected to keep the liquidity of the salts adduct. The mixture was heated to 60 C under reflux for 3-5 hours to form an amine hydrochloride salts. The reaction was monitored by AHV and TAV until the TAV was within 0-5 mg KOH/g. Amine hydrochloride salts had an AHV of 101.02 mg KOH/g and a TAV of 1.35 mg KOH/g. After 3-5 hours of reaction, 17.55 g of epichlorohydrin (0.97 mol) was added drop-wise to the reaction and was continued at 80 C for 5-7 hours to form N-(3- chloro-2-hydroxypropyl)-N,N-dimethyldodecan-1-aminium chloride (1:1) intermediate. Reaction was monitored by AHV and chloride titration. The intermediate had an AHV of 4.26 mg KOH/g and a chloride concentration of 5.17%. Reaction temperature was cooled down to 50-60 C prior to trimethylamine addition.21.25 g of trimethylamine, 50% solution in water (0.90 mol) was added dropwise into the reaction and was continued stirring for 3-5 hours at 70- 80 C. Reaction was monitored by chloride titration and TAV. The final product, N1-dodecyl-2- hydroxy-N1,N1,N3,N3,N3-pentamethylpropane-1,3-diaminium chloride (1:2), had an TAV of 3.22 mg KOH/g and a chloride concentration of 7.65%
1,2,4,5-tetrakis[(N-(1-dodecyl)-N,N-dimethylammoniummethyl)]benzene tetrabromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
In propan-1-ol; for 12h;
General procedure: 1,2,4,5-tetrakis-[N-(1-alkyl)-N,N-dimethylammoniummethyl]benzene tetrabromides (18-23) weresynthesized of 1 equivalent of 1,2,4,5-tetra(bromomethyl)benzene (0.5 g; 1.12 mmol) (1c) with 4equivalents (4.48 mmol) of N-hexyl-N,N-dimethylamine (0.58 g), N,N-dimethyl-N-octylamine (0.7 g),N-decyl-N,N-dimethylamine (0.83 g), N-dodecyl-N,N-dimethylamine (0.95 g), N,N-dimethyl-Ntetradecylamine(1.08 g), N-hexadecyl-N,N-dimethylamine (1.23 g), respectively, by heating in n-propanol from 7 h to 14 h. White solids were obtained. The crude products were purified byrecrystallization from a mixture of acetone/methanol (10:1) (Supplementary material).
Hexamethylene-1,6-bis(N,N-dimethyl-N-dodecylammonium bromide) (GS-12-6-12) was preparedby reaction of N,N-dimethyl-N-dodecylamine (36.4 g, 0.18 M) (Aldrich, Munich, Germany) with1,6-dibromohexane (21.4 g, 0.08 M) (Aldrich) in acetonitrile (120 mL) under reflux for 6 h, according to a procedure described in literature [25]. The crude product was crystallized from acetonitrile togive white crystals of GS-12-6-12 (Yield 90.4%, m.p. 231-232 °C; elemental analysis: found (calc.)%C 60.51 (60.88); %H 11.65 (11.12); %N 4.09 (4.18); ES + MS m/z 255 (C34H74N2/2). The purity of thesynthesized compound was confirmed by 1H-NMR (Figure 3) and 13C-NMR (Figure 4).
90.4%
In acetonitrile for 6h; Reflux;
3.2. Antimicrobial Agents
The antimicrobial agents used were n-dodecyltrimethylammonium bromide (DTAB), monomericalkylammonioum salt and hexamethylene-1,6-bis-(N,N-dimethyl-N-dodecylammonium bromide)(C6) dimeric alkylammonium salt. Dodecyltrimethylammonium bromide is commercially available(Aldrich, Munich, Germany), while the gemini surfactant (C6) was synthesized by the reaction ofN,N-dimethyl-N-dodecylamine (36.4 g, 0.18 M) (Aldrich, Munich, Germany) with 1,6-dibromohexane(21.4 g, 0.08 M) (Aldrich, Munich, Germany) in acetonitrile (120 mL) under reflux for 6 h, according toa procedure described in literature [19]. The crude product was crystallized from acetonitrile to givewhite crystals of C6 (Yield 90.4%, m.p. 231-232 °C; elemental analysis: found (calc.) %C 60.51 (60.88);%H 11.65 (11.12); %N 4.09 (4.18); ES + MS m/z 255 (C34H74N2/2).
89%
In neat (no solvent) at 20℃; for 0.5h; Green chemistry;
2.3.2. Synthesis without solvent
The mixture of N,N-dimethyl-N-dodecylamine (5325 g, 25 mmol)and 1,6-dibromohexane (3.05 g, 12.5 mmol) was stirred in room temperature for 0.5 h. Solidified product was crystallized from acetonitrile and dried over P4O10. Yield 89%, m.p. 231-232 °C, ESIMS m/z 255.
85%
In acetonitrile for 20h; Reflux;
84%
In acetonitrile for 5h; Reflux;
78%
In acetone for 24h; Reflux;
In acetone at 40℃;
In acetone for 48h; Reflux;
2.2. Synthesis of gemini surfactants
Gemini cationic surfactant N,N'-didodecyl-N,N,N',N'-tetramethyl-N,N'-hexanediyl-di-ammonium dibromide (G12-6-12) was synthesized according to literature refPreviewPlaceHolder[24]. To the solution of N,N-dimethyldodecylamine (10-15% excess) in dry acetone, was added 1,6-dibromohexane dropwise. The reaction mixture was then brought to reflux for 48 h. After cooling to room temperature, a white solid precipitated. The solid was obtained by filtration (washing with acetone) and then recrystallization from anhydrous ethanol.
The thermostatted reactor 1 with a heated jacket is filled with 120 ml of a rectified commercial tertiary amines mixture consisting essentially of dodecyl dimethylamine and tetradecyl dimethylamine. The mixture is heated to 40 C under continual stirring, after which benzyl chloride is added into the reactor in small portions, while the heat is gradually increased. As the temperature rises, the solution in the reactor grows turbid, and as the temperature reaches 74 C, the turbid white solution clarifies, but tinges a kind of yellow color and gelates resembling an oily liquid. As the temperature reaches 80 C, the mixture breaks down and a white milky layer appears on its surface, which disappears when a small quantity of benzyl chloride is added. The mass ratio of the tertiary amines mixture to benzyl chloride in this embodiment is 1.57:1. The mixture is aged in the reactor at a temperature of 80-90 C with the agitator operating at the rate of 200 rpm during 2.5 hours. Then the mixture is cooled to a room temperature. The cooling mixture rapidly gelates and congeals into a solid mass of buttercup yellow color with noticeable distinct globular inclusions. The received alkyldimethyl benzyl ammonium chloride consists essentially of dodecyl dimethylbenzyl ammonium chloride and tetradecyl dimethylbenzyl ammonium chloride, and alkyl radicals containing more than 14 carbon atoms were not found.Results of Impurities Content Analysis of Alkyldimethyl Benzyl Ammonium Chloride Gel [Table 2] No.CompoundYield time, minContent, mass %1Alkyldimethyl benzyl ammonium chloride94.892Benzyl chloride2.714.823Chlordecane5.610.064Dimethyl dodecanamine5.710.295Methylbenzyl dodecanamine9.060.04 As evidenced by data presented in Table 2, the derived product contains 94.89 mass percent of the base material, and the principal impurity is benzyl chloride, 4.82 mass %. This is due to the fact that benzyl chloride was taken for synthesis abundantly, and still it had no material effect on the product toxicity in general. The resultant gel features the same bactericidal effect as commercial disinfectants. Essentially, the gel can be used as a sanitizer immediately after synthesis, without any afterpurification.
The implementation as in Embodiment 2, with the exception that the reactor was additionally filled with water as a thinner. The derived product was a 50-percent solution of alkyldimethyl benzyl ammonium chloride consisting essentially of dodecyl dimethylbenzyl ammonium chloride and tetradecyl dimethylbenzyl ammonium chloride. Table 3 presents the results of the impurities content analysis of the product obtained according to Embodiment 5 (Specimen No. 2), and of the present-day commercial 50-percent aqueous solution (Specimen No. 1). The data presented in Table 3 show that the aqueous dimethylbenzyl ammonium chloride solution obtained according to Embodiment 5 contains approximately 1.5 times less impurities than the commercial solution, and its purity is 97.23 mass %, which is higher. The comparative results of the impurities content analysis of the commercial product and the product derived according to the invention. [] [] Thus, the proposed invention renders it possible to produce an effective, cheap and low-toxic sanitizer with the use of inexpensive and procurable raw materials, to save energy for its production, to vary the percentage of dimethyl dodecyl ammonium chloride and tetradecyl dimethylbenzyl ammonium chloride as required, as well as to use the synthesized product without further treatment.
8
EXAMPLE 1; A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass (on the basis of the raw amide compound) of the catalyst produced in Production Example 1. An inside of the autoclave was purged and replaced with nitrogen, and then hydrogen was introduced thereinto until an inside pressure of the autoclave reached 0.5 MPa. Thereafter, while maintaining the inside pressure of the autoclave at 0.5 MPa, hydrogen was introduced into the reaction system at a rate of 40 L/h (1.35 mol/h per 1 mol of the raw amide compound). Then, the reaction system was heated to 250°C at which the hydrogen reduction reaction was conducted for 6 h. The obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the reaction product was analyzed by gas chromatography. The composition of the thus obtained reaction product is shown in Table 1. EXAMPLES 3 TO 11 AND COMPARATIVE EXAMPLES 3 AND 4 The same procedure as in Example 1 was repeated except that the respective catalysts produced in Production Examples 3 to 11 and Comparative Production Examples 1 and 2 were used in place of the catalyst produced in Production Example 1, and the hydrogen reduction reaction was conducted for the time period as shown in Table 2 while maintaining the reaction pressure at 1.5 MPaG. The respective obtained reaction products were subjected to filtration to remove the catalysts therefrom, and the compositions thereof were analyzed by gas chromatography. The compositions of the respective reaction products are shown in Table 2.
With hydrogen at 230 - 250℃;
1; 9
EXAMPLE 1; A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass of the catalyst produced in Production Example 1 (on the basis of the raw amide). An inside of the autoclave was purged with nitrogen, and then hydrogen was introduced thereinto until an inside pressure of the autoclave was increased to 0.5 MPa. Thereafter, while maintaining the inside pressure of the autoclave at 0.5 MPa, hydrogen was introduced into the reaction system at a rate of 40 L/h (1.35 mol/h per 1 mol of the raw amide). Next, the reaction system was heated to 250°C at which the respective components were reacted with each other, and the reaction product was sampled when the amount of the raw amide was reduced to 1%. The thus sampled reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated reaction solution was analyzed by gas chromatography. The composition of the final reaction product is shown in Table 2.; EXAMPLE 9 A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass of the catalyst produced in Production Example 1 (on the basis of the raw amide). While maintaining the reaction pressure at 5 MPa, hydrogen was introduced into the reaction system at a rate of 40 L/h (1.35 mol/h per 1 mol of the raw amide). Next, the respective components were reacted with each other at a temperature as shown in Table 3, and the reaction product was sampled when the amount of the raw amide was reduced to 1%. The thus sampled reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated reaction solution was analyzed by gas chromatography. The composition of the final reaction product is shown in Table 3.
With hydrogen at 230 - 250℃;
4
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.
With hydrogen at 250℃;
2; 13
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.; EXAMPLE 13 A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass of the catalyst produced in Production Example 2 (on the basis of the raw amide). While maintaining the respective reaction pressures as shown in Table 4, hydrogen was introduced into the reaction system at a rate of 40 L/h (1.35 mol/h per 1 mol of the raw amide). Next, the respective components were reacted with each other at 250°C, and the reaction product was sampled when the amount of the raw amide was reduced to 1%. The thus sampled reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated reaction solution was analyzed by gas chromatography. The composition of the final reaction product is shown in Table 4.
With hydrogen at 230 - 250℃;
5; 11
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.; EXAMPLES 10 TO 12 AND COMPARATIVE EXAMPLE 3 The same procedure as in Example 9 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 3 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 3.
With hydrogen at 230 - 250℃;
7; 12
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.; EXAMPLES 10 TO 12 AND COMPARATIVE EXAMPLE 3 The same procedure as in Example 9 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 3 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 3.
With hydrogen at 230 - 250℃;
3; 10
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.; EXAMPLES 10 TO 12 AND COMPARATIVE EXAMPLE 3 The same procedure as in Example 9 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 3 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 3.
With hydrogen at 250℃;
8
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.
With hydrogen at 250℃;
6
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.
With hydrogen at 250℃;
2
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.
With hydrogen at 230 - 250℃;
1; 3; 4
EXAMPLES 2 TO 8 AND COMPARATIVE EXAMPLES 1 AND 2 The same procedure as in Example 1 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 2 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 2.; EXAMPLES 10 TO 12 AND COMPARATIVE EXAMPLE 3 The same procedure as in Example 9 was repeated except for using 5% by mass (on the basis of the raw amide) of the respective catalysts as shown in Table 3 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 1 upon conducting the reaction. The compositions of the respective final reaction products are shown in Table 3.; COMPARATIVE EXAMPLE 4 The same procedure as in Example 13 was repeated except for using 5% by mass (on the basis of the raw amide) of the catalyst obtained in Comparative Production Example 1 in place of 5% by mass (on the basis of the raw amide) of the catalyst obtained in Production Example 2 upon conducting the reaction. The composition of the final reaction product is shown in Table 4.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 230 - 250℃; for 6 - 9h; Autoclave;
Stage #2: With dimethyl amine for 1 - 3h;
1; 2; 3
A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass of the catalyst produced in Production Example 1 (on the basis of the raw amide compound). An inside of the autoclave was purged with nitrogen, and then hydrogen was introduced thereinto until an inside pressure of the autoclave was increased to 1.5 MPaG. Thereafter, while maintaining the inside pressure of the autoclave at 1.5 MPaG, hydrogen was introduced into the reaction system at a rate of 40 L/h (1.4 mol/h per 1 mol of the raw amide compound). Next, the reaction system was heated to 2300C at which the hydrogen-reduction reaction was carried out until no raw amide compound was detected therein as measured by gas chromatography. The reaction rate upon the above reaction was shown in Table 1. Meanwhile, the reaction rate was calculated from a hourly ratio of the amount of the amide compound reacted for six hours from initiation of the reaction as measured by gas chromatography to the whole amount of the raw amide compound charged [(amount (mol) of the amide compound reacted per 1 hour)/( whole amount (kg) of the raw amide compound charged)] (this definition is also applied to the subsequent Examples). Next, while maintaining the same reaction temperature and pressure as well as the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 2 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.; EXAMPLE 2The hydrogen-reduction reaction was conducted in the same manner as in Example 1 except for using the catalyst produced in Production Example 2 in place of the catalyst produced in Production Example 1 and changing the reaction temperature to 2500C. As a result, 9 hours after initiation of the reaction, the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit. The reaction rate upon the above reaction was shown in Table 1. Next, while maintaining the same reaction temperature and pressure as well as the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 1 to 0.4 L/h (from 0.03 to 0.01 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 1 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.; EXAMPLE 3The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 2 except that the amount of the catalyst used was changed from 5% by mass to 3% by mass (on the basis of the raw amide compound). The reaction rate upon the above reaction was shown in Table 1. Next, while maintaining the same reaction temperature and pressure as well as the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 3 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.
With hydrogen at 230℃; Autoclave;
2
The reaction was conducted in the same manner as in Comparative Example 1 except for using a commercially available Cu-Cr catalyst ("Cu 180Op" available from N.E. Chemcat Corp.) in place of the catalyst produced in Production Example 7 and introducing hydrogen at a rate of 40 L/h (1.4 mol/h per 1 mol of the raw amide compound). The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. As a result, it was confirmed that the amount of dimethyl lauroyl amide contained in the reaction product was below the lower detection limit, and the reaction product was composed of 82.9% of dimethyl lauryl amine, 12.4% of dilauryl methyl amine and 0.6% of lauryl alcohol. Further, the reaction rate upon the above reaction was 36.4 [x 10'2 mol/(kg-h)].
With hydrogen at 230℃; Autoclave;
1
A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and 5% by mass of the catalyst produced in Production Example 7 (on the basis of the raw amide compound). An inside of the autoclave was purged with nitrogen, and then hydrogen was introduced thereinto until an inside pressure of the autoclave was increased to 1.5 MPaG. Thereafter, while maintaining the inside pressure of the autoclave at 1.5 MPaG, hydrogen and dimethyl amine were introduced into the reaction system at rates of 70 L/h (2.4 mol/h per 1 mol of the raw amide compound) and from 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), respectively, and the resultant mixture was reacted. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 2. Meanwhile, as a result of analyzing the composition of the reaction product, it was confirmed that the amount of dimethyl lauroyl amide was below the lower detection limit.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 250℃; Autoclave;
Stage #2: With dimethyl amine at 220℃; for 1h;
3
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 10 except for using a commercially available Cu-Cr catalyst ("Cul800p" available from N.E. Chemcat Corp.) in place of the commercially available Cu-Zn catalyst. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. As a result, it was confirmed that the amount of dimethyl lauroyl amide contained in the reaction product was below the lower detection limit, and the reaction product was composed of 79.8% of dimethyl lauryl amine, 9.4% of dilauryl methyl amine and 5.3% of lauryl alcohol.Further, the reaction rate upon the above reaction was 45.1 [x 10"2 mol/(kg-h)]. Next, after changing the reaction pressure to normal pressures but while maintaining the same reaction temperature and hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 9 to 8 L/h (from 0.30 to 0.27 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for I h. As a result, it was confirmed that the reaction product was composed of 84.4% of dimethyl lauryl amine, 9.6% of dilauryl methyl amine and 0.8% of lauryl alcohol.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 250℃; Autoclave;
Stage #2: With dimethyl amine at 220℃; for 3h;
10
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 4 except for using a commercially available Cu-Zn catalyst ("Cu0890p" available from N.E. Chemcat Corp.) in place of the catalyst produced in Production Example 3. The reaction rate upon the above reaction was shown in Table 3. Next, after changing the reaction pressure to normal pressures but while maintaining the same reaction temperature and hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 9 to 8 L/h (from 0.30 to 0.27 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 3 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 3.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 250℃; Autoclave;
Stage #2: With dimethyl amine at 220℃; for 3h;
5
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 4 except for using the catalyst produced in Production Example 4 in place of the catalyst produced in Production Example 4. The reaction rate upon the above reaction was shown in Table 1. Next, after changing the reaction pressure to 0.5 MPaG but while maintaining the same reaction temperature and hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 3 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 230℃; Autoclave;
Stage #2: With dimethyl amine for 3h;
6
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 1 except for using the catalyst produced in Production Example 5 in place of the catalyst produced in Production Example 1 and maintaining the reaction temperature and pressure at 2300C and 5.0 MPaG, respectively. The reaction rate upon the above reaction was shown in Table 1. Next, after changing the reaction pressure to 3.0 MPaG but while maintaining the same reaction temperature and hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 3 to 2 L/h (from 0.1 to 0.07 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 3 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 250℃; Autoclave;
Stage #2: With dimethyl amine at 220℃; for 2h;
4
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 1 except for using the catalyst produced in Production Example 3 in place of the catalyst produced in Production Example 1 and maintaining the reaction temperature and pressure at 2500C and 1.5 MPaG, respectively. The reaction rate upon the above reaction was shown in Table 1. Next, after changing the reaction temperature to 2200C and the reaction pressure to normal pressures but while maintaining the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 3 to 2 L/h (from 0.10 to 0.07 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 2 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 250℃; Autoclave;
Stage #2: With dimethyl amine at 220℃; for 1h;
7
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 1 except for using the catalyst produced in Production Example 6 in place of the catalyst produced in Production Example 1 and maintaining the reaction temperature and pressure at 2500C and 0.5 MPaG, respectively. The reaction rate upon the above reaction was shown in Table 1. Next, after changing the reaction temperature to 220°C and the reaction pressure to normal pressures but while maintaining the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 3 to 2 L/h (from 0.10 to 0.07 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 1 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 1.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 250℃; Autoclave;
Stage #2: With dimethyl amine at 220℃; for 3h;
9
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 4 except for using the catalyst produced in Production Example 8 in place of the catalyst produced in Production Example 3. The reaction rate upon the above reaction was shown in Table 3. Next, after changing the reaction pressure to 0.2 MPaG but while maintaining the same reaction temperature and hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 3 to 2 L/h (from 0.10 to 0.07 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 3 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 3.
Stage #1: N,N-dimethyldodecanamide With hydrogen at 230℃; Autoclave;
Stage #2: With dimethyl amine at 180℃; for 2h;
8
The hydrogen-reduction reaction was conducted until the amount of the raw amide compound as measured by gas chromatography was reduced below the lower detection limit, in the same manner as in Example 1 except for using the catalyst produced in Production Example 7 in place of the catalyst produced in Production Example 1 and introducing hydrogen into the reaction system at a rate of 70 L/h (2.4 mol/h per 1 mol of the raw amide compound). The reaction rate upon the above reaction was shown in Table 2. Next, after changing the reaction temperature to 18O0C and the reaction pressure to 0.2 MPaG but while maintaining the same hydrogen introduction rate, dimethyl amine was additionally introduced to the reaction system at a rate of 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), and the resultant mixture was reacted for 2 h. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated product solution was analyzed by gas chromatography. The results are shown in Table 2.
Stage #1: N,N-dimethylaminododecane; chloroacetonitrile In ethyl acetate at 50 - 60℃; for 6h;
Stage #2: methyl para-dodecylbenzenesulfonate In ethyl acetate at 80℃; for 1.5h;
6 Synthesis of (cyanomethyl)dimethyldodecylammonium Para-Dodecylbenzenesulfonate
Example 6 Synthesis of (cyanomethyl)dimethyldodecylammonium Para-Dodecylbenzenesulfonate 213.4 g (1 mol) of dimethyldodecylamine were initially charged at 50° C. in 500 ml of ethyl acetate, and 75.5 g (1 mol) of chloroacetonitrile were added. The reaction mixture was stirred at 60° C. for 6 hours. Then 340.52 g (1 mol) of methyl para-dodecylbenzenesulfonate were added and the reaction mixture was stirred at 80° C. for 90 minutes, in the course of which vigorous evolution of gas was observed. The reaction mixture was cooled slowly to 5° C., and the precipitated solid was washed twice with 50 ml each time of ethyl acetate and dried at 60° C. under reduced pressure. 504.5 g (0.89 mol) of (cyanomethyl)dimethyldodecylammonium para-dodecylbenzenesulfonate were obtained as a colorless solid, corresponding to a yield of 89%. 1H NMR (CDCl3): δ=7.73 (2H, d); δ=7.16 (2H, d); δ=5.32 (2H, s); δ=3.58 (2H, t); δ=3.47 (6H, s); δ=1.75 (2H, m); δ=1.68-1.45 (4H, m); δ=1.33-1.0 (36H, m); δ=0.87 (6H, t).
(cyanomethyl)dimethyldodecylammonium methysulfate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
Stage #1: N,N-dimethylaminododecane; chloroacetonitrile In toluene at 50 - 60℃; for 6h;
Stage #2: dimethyl sulfate In toluene at 80℃; for 1.5h;
5 Synthesis of (cyanomethyl)dimethyldodecylammonium Methylsulfate
Example 5 Synthesis of (cyanomethyl)dimethyldodecylammonium Methylsulfate 113.4 g (1 mol) of dimethyldodecylamine were initially charged at 50° C. in 1000 ml of toluene and 75.5 g (1 mol) of chloroacetonitrile were added. The reaction mixture was stirred at 60° C. for 6 hours. Then 126.13 g (1 mol) of dimethyl sulfate were added and the reaction mixture was stirred at 80° C. for 90 minutes, in the course of which vigorous evolution of gas was observed. The reaction mixture was cooled slowly to 5° C., and the precipitated solid was washed twice with 50 ml of toluene each time and dried at 60° C. under reduced pressure. 335.39 g (0.92 mol) of (cyanomethyl)dimethyldodecylammonium methylsulfate were obtained as a colorless solid, corresponding to a yield of 92%. 1H NMR (D2O): δ=4.75 (2H, s); δ=3.75 (3H, s); δ=3.59 (2H, t); δ=3.39 (6H, s); δ=1.90 (2H, m); δ=1.45-1.30 (18H, m); δ=0.92 (3H, t).
With hydrogen; dimethyl amine In water at 250℃; Inert atmosphere; Autoclave;
3
Comparative Example 3A rotary autoclave was charged with 300 g of N,N-dimethyl lauroyl amide and a Cu/Cr catalyst “Cu 1800p” commercially available from N.E. Chemcat Corp. An inside of the autoclave was purged with nitrogen, and then hydrogen was introduced thereinto until an inside pressure of the autoclave was increased to 1.5 MPaG. Thereafter, while maintaining the inside pressure of the autoclave at 1.5 MPaG, hydrogen and dimethyl amine were introduced into the reaction system at rates of 40 L/h (1.4 mol/h per 1 mol of the raw amide compound) and from 2 to 1 L/h (from 0.07 to 0.03 mol/h per 1 mol of the raw amide compound), respectively, and the resultant mixture was reacted. The thus obtained reaction product was subjected to filtration to remove the catalyst therefrom, and then the composition of the thus separated reaction solution was analyzed by gas chromatography. As a result, it was confirmed that the content of N,N-dimethyl lauroyl amide in the reaction product was below the lower detection limit, and the reaction product was composed of 82.9% of N,N-dimethyl lauryl amine, 12.4% of N,N-dilauryl methyl amine and 0.6% of lauryl alcohol. Further, it was confirmed that the reaction rate at the time at which 6 hours elapsed from initiation of the reaction was 36.4 [×10-2 mol/kg·H)], and the amount of N,N-dimethyl lauryl amine produced when the amount of the raw amide was reduced to 5% was 78.4 (% by mass).
In water at 70 - 100℃; for 14.5h; Inert atmosphere;
antimicrobial quaternary ammonium chloride (A), where n = 11 , m = 2, was prepared by mixing 85.36 grams of N,N-dimethyldodecylamine and 67.6 grams of deionized water in a 500ml three neck round-bottomed flask equipped with an additional funnel, reflux condenser and a magnetic stirrer. The mixture was heated to 700C under nitrogen and 49.83 grams of 2-(2- chloroethoxy)ethanol was then added to the reaction mixture over 0.5 hrs. The reaction was heated to refluxing (~100°C) temperature and was kept for 14 hrs. A clear gel like mass was obtained after cooling to room temperature. The crude product was dried with a rotavap at 800C, dissolved in warm acetone, and re-crystallized at about 3°C. The white crystalline powder obtained from this step was re-crystallized from warm acetone again to remove any impurity and starting materials. To remove residual water, the crystalline power was further re-crystallized from Acetone/THF (8/3, v/v) solvent mixture. The total yield was about 80 %. FTIR and NMR characterization confirmed the structure and purity of > 99%. See Figure 1. Karl Fischer water titration indicated 0.12 % of residual water, since the compound is used in small amounts (<2%) in the synthesis, the impact to overall water content is low enough for the typical polyurethane reaction.
N,N'-didodecyl-N,N,N',N'-tetramethyl-N,N'-(p-xylenediyl)diammonium dibromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
99%
In acetone for 12h; Reflux;
N,N'-Didecyl-N,N,N',N'-Tetramethyl-N,N'-Ethanediyl-Diammonium Dibromide (10-2-10)
General procedure: A magnetically stirred solution of N,N,N0,N0-tetramethylethylenediamine(4.64 g, 40 mmol) and 1-bromodecane(17.68 g, 80 mmol) in 200 mL of acetone was refluxed for 12 h. Then the mixture was cooled and was left for 12 h in cold conditions. The crude product was precipitated in the form of white crystals. It was recrystallized two times from acetone then filtered and dried in air, yielding 10.4 g of white crystals (47 %).
95%
In propan-1-ol for 9h;
Series of dimeric quaternary ammonium salts (2-9)
General procedure: 1,4-bis-[N-(1-alkyl)-N,N-dimethylammoniummethyl]benzene dibromides (2-9) were synthesizedof 1 equivalent of 1,4-di(bromomethyl)benzene (0.5 g; 1.89 mmol) (1a) with 2 equivalents (3.78mmol) of N-butyl-N,N-dimethylamine (0.38 g), N-hexyl-N,N-dimethylamine (0.49 g), N,N-dimethyl-Noctylamine(0.59 g), N-decyl-N,N-dimethylamine (0.7 g), N-dodecyl -N,N-dimethylamine(0.81 g), N,N-dimethyl-N-tetradecylamine (0.91 g), N-hexadecyl -N,N-dimethylamine (1.02 g),N,N-dimethyl-N-octadecylamine (1.13 g), respectively, by heating in n-propanol from 4 h to 10 h.White solids were obtained. The crude products were purified by recrystallization from a mixture ofacetone/methanol (10:1) (Supplementary material).
ethane-1,2-diyl bis(N,N-dimethyl-N-dodecylammoniumacetoxy) dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
92%
for 0.166667h; Microwave irradiation;
In the second step, a mixture of the as-prepared spacer EDBC (10mmol) and N,N-dimethyldodecylamine (NNDAD) (20mmol) in a 10mL microwave vessel was irradiated by microwave at power 450W for 10min (15s×40). The crude solid product was washed with diethyl ether and further purification was achieved by recrystallization from ethyl acetate-ethanol mixture to obtain the white powder of DCGS. The characterization data of DCGS are given below: White solid, 92% yield, m. p.: 191-193°C, FT-IR (KBr): 2989 (C-H), 2852 (C-H), 1744 (C=O), 1462 (C-O), 1199 (C-N) cm-1.1H NMR (500MHz, DMSO-d6): 0.763 (6H, CH3), 1.24 (40H, -(CH2)10×2, alkyl chain), 3.4 (12H, -N+(CH3)2×2), 3.5 (4H, -N+CH2×2), 4.2 (4H, -N+CH2COO×2), 4.4 (4H, -CH2O×2).
78.6%
In ethyl acetate for 10h; Reflux;
39%
In dichloromethane; ethyl acetate for 12h; Reflux; Inert atmosphere;
In ethyl acetate for 10h; Reflux;
In ethyl acetate for 10h; Reflux;
In ethyl acetate for 10h;
2.2.1. Synthesis route of the biocompatible gemini surfactants
General procedure: In the second step, the desired gemini was synthesized by heating ethane-1,2-diyl bis(chloroacetate) with N, N-dimethylalkylamine(molar ratio=1:2.1) in ethyl acetate for 10 h. The solvent was removed under reduced pressure and white crystalline solid of the final product was obtained. The product was recrystallized in ethyl acetate-ethanol mixture (5:1) and was obtained in good yield. The purity and structure confirmation of the gemini surfactants (m-E2-m) were done via some analytical methods like Silica gel thin layer plate chromatography(TLC), elemental (C, H, N) analysis, FT-IR, 1H NMR and ESI-MS (+) spectroscopy.The presence of no minima in the surface tension versus log[surfactant] plots was taken as additional evidence regarding the purityof the surfactants. The synthesis protocol is illustrated in Scheme 2.Some important properties of m-E2-m are presented in Table 1.
In dichloromethane at 90 - 100℃; for 10h;
2.2 Example 2
2) 1 part of the above prepared ethylene glycol chloroacetate and 2.5 parts of N, N-dimethyl dodecanamine added to the reactionThen, an appropriate amount of dichloromethane was added as a solvent, and the mixture was refluxed at 90-100 ° C for 10 hours to obtain an ester group-containing Gemini quaternary ammonium salt.
In acetone at 45℃; for 14h;
1.2
Take 6.40g of N,N-dimethyldodecane-1-amine into a three-necked flask, add 25mL of acetone, and then add 2.58g of ethane-1,2-diylbis(2-chloroacetic acid) and 25mL of acetone. After mixing acetone, it was added dropwise to a three-necked flask at a rate of 1-2 seconds/drop, refluxed at 45°C for 14 hours, suction filtered, and the product was recrystallized and purified with a mixture of DCM and petroleum ether with a volume ratio of 1:5. , and dried under vacuum at 50°C to obtain the product, the dibasic ester quaternary ammonium salt Q12-2-12.
With potassium hydroxide; In water; at 95℃; for 3.58333h;
Example 10[0139]This example was done in the same device as that of example 8, under the following conditions:[TABLE-US-00015] Q1Q2Q3T1 (mL/min)(mL/min)(mL/min)( C.)t1 (min)T2 ( C.)t2 (min)1.30.632.24951409575[0140]A betaine aqueous solution was then obtained at the outlet of the second reactor having the following characteristics:[TABLE-US-00016] Residual MCAResidual amineGlycolic acid(wt %)(wt %)(wt %)1.21.651.2
Adding chloroacetic acid to D101 in a predetermined amount and neutralizing chloroacetic acid to pH 8 in a sodium hydroxide solution of the same substance to obtain sodium chloroacetate. And then adding the amount of dodecyl dimethyl tertiary amine in the same amount at a temperature of 80 C for 6 hours.
General procedure: A tertiary amine (4d-k) (0.1 mol) and THF (100 mL) were charged into a three-necked round-bottom flask(250 mL). CGS (3) (15.4 g, 0.1 mol) in THF (30 mL) was added dropwise over50 min and the temperature increased to 34 °C. The reaction mixture was stirred for 2 to 24 h depending onthe amine at room temperature. The resulted whiteprecipitate was then filtered, washed with THF and dried in vacuo to afford the desired sulfate betaines (1d-k).
7.9 g
In tetrahydrofuran Reflux;
3 Example 3 : Application example
Example 3 : Application example7.64g of N, N-dimethyldodecan-1 -amine and 25ml of THF were charged into a 50ml of three-necked round-bottomed flask, 5.36g of CGS (compound of formula (?)) (in 10ml of THF) was added dropwise into it in about l Omins, then it was heated with an oil bath to reflux and stirred for sometime. Many bubbles were observed in the bottom of the flask. Then the reaction mixture was cooled to room temperature and filtered, washed with THF, and dried. 7.9g of the following sulfate betaine as white solid was obtained. HOCH2CH(OS03")CHN+(CH3)2(CH2)I 1CH3? NMR (DMSO-d6) of the end product of this reaction (CDCl3j 500 MHz), ?: 5.1 (m, 1H); 4.5 (m, 1 H); 3.75 (m, 1H); 3.3-3.51 (m, 4H); 3.1 (d, 6H); 1.61 -1.69 (m, 2H); 1.29 (m, 18H); 0.84 (t, 3H).
7.9 g
In tetrahydrofuran Reflux;
2
[086] 7.64 g of N, N-dimethyldodecan-1 -amine and 25 ml of THF were charged into a 50 ml of three-necked round-bottomed flask, 5.36 g of CGS as obtained from Example 1 (in 10 ml of THF) was added dropwise into it in about 10 mins, then it was heated with an oil bath to reflux and stirred for sometime, many bubbles in the bottom, followed with Ή-NMR, then it was cooled to room temperature and filtered, washed with THF, dried, 7.9 g of white solid was obtained as shown below. [087] 1 H-NMR (CDC13} 500 MHz) is shown as in Fig. 2.
7.9 g
In tetrahydrofuran Reflux;
2
7.64 g of N,N-dimethyldodecan-1-amine and 25 ml of THF were charged into a 50 ml of three-necked round-bottomed flask, 5.36 g of CGS as obtained from Example 1 (in 10 ml of THF) was added dropwise into it in about 10 mins, then it was heated with an oil bath to reflux and stirred for sometime, many bubbles in the bottom, followed with 1H-NMR, then it was cooled to room temperature and filtered, washed with THF, dried, 7.9 g of white solid was obtained as shown below. [0093] 1H-NMR (CDCl3, 500 MHz) is shown as in FIG. 2.
With 5%-palladium/activated carbon In water; toluene at 110℃; for 40h; Inert atmosphere;
Typical Experimental Procedure
General procedure: A mixture of o-phenylenediamine (1) (0.108 g, 1 mmol), tributylamine (2a) (0.185g, 1 mmol), 5% Pd/C (0.106 g, 0.05 mmol) and toluene/H2O (10 mL/0.5 mL) was placed in 25 mL round bottom flask. After the system was flushed with Ar from an Ar balloon connected to the flask via a reflux condenser, the reaction mixture was allowed to react at 110 oC for 20 h. The reaction mixture was filtered through a short silica gel column (ethylacetate-hexane mixture) to eliminate catalyst residue. Removal of the solvent left a crude mixture, which was separated by thin layer chromatography (silica gel, ethyl acetate-hexanemixture = 1/1) to give 2-propylbenzimidazole (3a) (0.115 g,72%). All products are known and several selected spectroscopic data are shown below.
N-[2-(methacryloyloxy)ethyl]-N,N-dimethyldodecane ammonium bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
In ethanol; at 70℃; for 24h;
In a 20 mL scintillation vials were added 10 mmol of DMAD (Tokyo Chemical Industry), 10 mmol of BEMA, and 3 g of ethanol. A magnetic stir bar was added, and the vial was capped and stirred at 70C for 24 h. After the reaction was complete, the solvent was removed via evaporation.
With tetrabutylammomium bromide In ethanol at 30℃; for 18h;
7; 8
General procedure: Example 7 Synthesis of the gemini type biocidal compound of the present invention using phase-transfer catalysis . The experimental procedure described below allows obtaining the compound of the present invention (and is shown in Figure 1) . A 50-mL flask equipped with a condenser and magnetic stirrer was used to obtain the biocidal compound of the present invention. To a mixture of ethanol (2.5 mL) , 2-0- acetyl-1 , 3-dichloropropane (2) (0.923 g, 5.40 mmol) and tetrabutylammonium bromide (TBABr) (0.034 g, 0.108 mmol), the corresponding amine (N, iV-dimethyldodecylamine 2.305 g, N, iV-dimethylfarnesylamine 2.667 g, N, N-dimethyl- perfluorooctyl-propylamine 5.432 g, N, N- dipropenyldodecylamine 2.863 g, N, N- dipropenylfarnesylamine 3252 g, and N, iV-dipropenyl- perfluorooctyl-propylamine (6.017 g, 10.8 mmol) were added. The reaction mixture was maintained at a temperature of 30 °C for 18 hours with magnetic stirring. After the reaction (disappearance of (2) displayed by thin-layer chromatography (TLC) , ethanol was evaporated with the aid of a rotary evaporator and then vacuum was applied to ensure complete removal of solvent. Afterwards, the purification of the target compounds was performed using adsorption chromatography on silica gel, and the following mixed solvents were used as eluent : ethyl acetate/ethanol/distilled water/28 to 30% ammonium hydroxide (4:1:0.25:0.5) . Then, the solvent mixture was evaporated under reduced pressure. Finally, the dicationic gemini 3a-c and 4a-c were obtained as pure compounds isolated in 92, 91, 96% (3a-c) , and 92, 94 and 97% (4a-c) respectively.
2,2′-[(oxybis(ethane-1,2-diyl))bis(oxy)]bis(N-dodecyl-N,N-dimethyl-2-oxoethanaminium) dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
96.2%
In acetone for 24h; Reflux; Green chemistry;
Synthesis of Ethylene Glycol Bisacetyl-α,ω-bis(dimethylalkylammonium Choride) (Step 2: Quaternization)
General procedure: Dodecyldimethyl tertiary amine, tetradecyldimethyl tertiary amine, or hexadecyldimethyl tertiary amine (0.36 mol) and acetone (50 g) were added into a 250-mL flask equipped with a reflux condenser fixed on a magnetic stirrer. The solution mixture was stirred and then the glycol-bis(2-chloroethanoate) (0.15 mol) was added to the flask. After refluxing for 24 h, the mixture was placed at 4 °C until the product precipitated. The precipitate was washed several times with petroleum ether. It was dried in a vacuum oven at 45 °C for 12 h to remove any trapped solvents to give the final product. The yellow viscous liquids [G12-A2A-12, 96.2 % yield based on diethylene glycol-bis(2-chloroethanoate); G12-A3A-12, 95.1 % yield based on triethylene glycol-bis-(2-chloroethanoate); G12-A4A-12, 93.5 % yield based on tetraethyleneglycol-bis(2-chloroethanoate); G14-A2A-14, 92.9 % yield based on diethylene glycol-bis(2-chloroethanoate); and G16-A2A-16, 91.3 % yield based on diethylene glycol-bis(2-chloroethanoate)] were obtained [24, 25] (Scheme 1).
A mixture of a 38% aqueous solution of dimethylamine (12.5 mL, 93.8 mmol) and dodecyl bromide (11.7 g, 46.9 mmol) in benzene (15 mL) was stirred at 20-25 C for 20 h. Then, a 50% aqueous solution of NaOH (1.9 g, 46.9 mmol) was added to the reaction mixture, and the resulting mixture was evaporated in vacuo. The residue was dissolved in CHCl3 (20 mL), the formed precipitate was filtered off, and the filtrate was evaporated in vacuo. According to the 1H NMR spectral data, the isolated mixture contained amine 6a (4.1 g, 40%), N,N-didodecyl-N,N-dimethylammonium bromide (4.9 g, 46%), and unreacted dodecyl bromide (1.7 g, 14%).
Synthesis ofsurfactants(denoted asCn-1EC-s-Cm)
General procedure: 5 mmol 3-alkyl acyloxy-2-hydroxy chloropropane and5.5 mmol N,N-dimethyldodecylamine (1.17 g)/ N,Ndimethyltetradecylamine(1.33 g)/ N,Ndimethylhexadecylamine(1.48 g)were dissolved in 35 mLethanol in a 100 mL round flask. The reaction solution waskept at 85oC for about 24 h. Excess ethanol was removedunder vacuum and the residue was recrystallized twice from ethyl acetate / diethyl ether, the products were obtained aswhite amorphous powder.
62%
In ethanol at 85℃; for 24h;
Synthesis ofsurfactants(denoted asCn-1EC-s-Cm)
General procedure: 5 mmol 3-alkyl acyloxy-2-hydroxy chloropropane and5.5 mmol N,N-dimethyldodecylamine (1.17 g)/ N,Ndimethyltetradecylamine(1.33 g)/ N,Ndimethylhexadecylamine(1.48 g)were dissolved in 35 mLethanol in a 100 mL round flask. The reaction solution waskept at 85oC for about 24 h. Excess ethanol was removedunder vacuum and the residue was recrystallized twice fromethyl acetate / diethyl ether, the products were obtained aswhite amorphous powder.
Synthesis ofsurfactants(denoted asCn-1EC-s-Cm)
General procedure: 5 mmol 3-alkyl acyloxy-2-hydroxy chloropropane and5.5 mmol N,N-dimethyldodecylamine (1.17 g)/ N,Ndimethyltetradecylamine(1.33 g)/ N,Ndimethylhexadecylamine(1.48 g)were dissolved in 35 mLethanol in a 100 mL round flask. The reaction solution waskept at 85oC for about 24 h. Excess ethanol was removedunder vacuum and the residue was recrystallized twice from ethyl acetate / diethyl ether, the products were obtained aswhite amorphous powder.
72%
In ethanol at 85℃; for 24h;
Synthesis ofsurfactants(denoted asCn-1EC-s-Cm)
General procedure: 5 mmol 3-alkyl acyloxy-2-hydroxy chloropropane and5.5 mmol N,N-dimethyldodecylamine (1.17 g)/ N,Ndimethyltetradecylamine(1.33 g)/ N,Ndimethylhexadecylamine(1.48 g)were dissolved in 35 mLethanol in a 100 mL round flask. The reaction solution waskept at 85oC for about 24 h. Excess ethanol was removedunder vacuum and the residue was recrystallized twice fromethyl acetate / diethyl ether, the products were obtained aswhite amorphous powder.
Stage #1: N,N-dimethylaminododecane; methyl chloroacetate at 20℃; for 12h; Inert atmosphere;
Stage #2: With hydrogenchloride In water for 1h; Reflux;
2.2. Catalyst preparation
General procedure: The BAILs were prepared according to reported procedures [41]. A typical synthesis route of [(CH2COOH)DMDA]Br (5a) is as follows. Under an inert atmosphere of N2, a mixture of N,N-dimethyldodecylamine (0.01 mol, 1.27 mL) and methyl bromoacetate (0.01 mol, 0.6 mL) was stirred at room temperature for 12 h, during which time the reaction mixture turned into a solid. A mixture of the solid and HCl (37% H2O solution,0.012 mol) was refluxed for 1 h. The solvent was removed under vacuum, and the remaining solid was washed three times with cold diethyl ether to give the product as a white powder. [(CH2COOH)DMDA]Cl (5b). mp 150-152 °C, yield 95%, awhite solid;
Stage #1: N,N-dimethylaminododecane; bromoacetic acid methyl ester at 20℃; for 12h; Inert atmosphere;
Stage #2: With hydrogenchloride In water for 1h; Reflux;
2.2. Catalyst preparation
General procedure: The BAILs were prepared according to reported procedures [41]. A typical synthesis route of [(CH2COOH)DMDA]Br (5a) is as follows. Under an inert atmosphere of N2, a mixture of N,N-dimethyldodecylamine (0.01 mol, 1.27 mL) and methyl bromoacetate (0.01 mol, 0.6 mL) was stirred at room temperature for 12 h, during which time the reaction mixture turned into a solid. A mixture of the solid and HCl (37% H2O solution,0.012 mol) was refluxed for 1 h. The solvent was removed under vacuum, and the remaining solid was washed three times with cold diethyl ether to give the product as a white powder. [(CH2COOH)DMDA]Br (5a). mp 140-141 °C, yield 95%, awhite solid;
General procedure: The cationic gemini surfactants (m-E2-m,m=12, 14, 16)were synthesized as outlined in Scheme 1 which contained two main steps [3].The first step involves preparation of the spacer part, i.e., ethane-1,2-diyl bis(chloroacetate), by heating a mixture of chloroacetyl chloride(0.22 mol) and ethylene glycol (0.1 mol) in a round bottom flask at 323.15 K for 8 h in nitrogen atmosphere. The product was washed with saturated brine (NaCl) solution till complete neutralization. The product was dissolved in diethyl ether and magnesium sulphate was added to it for drying. After few hours the dissolved compound was separated from magnesium sulphate and needle shaped crystals were obtained on standing. In the second step, the gemini surfactant was obtained by heating the product of step one with the respective amine(N,N-dimethylalkylamine) (molar ratio = 1:2.1) in ethyl acetate for 10 h. Afterward, the solvent was removed under reduced pressure.The crude products were recrystallized in ethyl acetate-ethanol mixture(5:1). The surfactants were characterized by various analytical methods such as elemental analysis, 1HNMR, FT-IR and ESI-MS (+) spectroscopy(Figs. S1 to S6 and Table S1, Supporting information).
The CnGlu analogues were synthesized in our laboratory via a reaction of glutamic acid with octa-, deca-, dodeca-, tetradeca-,or hexadecanoyl chloride in the presence of triethylamine. C12DMA was purchased from Tokyo Chemical Industry and used without further purification. The acid-type CnGlu (1 equiv) was mixed with C12DMA (3 equiv) in ethanol at room temperature for 48 h under magnetic stirring. Then, the solvent was evaporated. The residue was recrystallized from either acetone or a mixture of hexane/ethyl acetate. After filtration, the residue was dried under reduced pressure. We confirmed the formation of a 1:1 stoichiometric complex of CnGlu-C12DMA on the basis of 1H NMR (JEOL-ECP 500 MHz) and ESI-MS (FT-ICR MS Varian 910-MS) data. These characterization data are shown in Supporting Information, Table S1. In typical experiments, the complex (3 wtpercent) was mixed with a NaOH aqueous solution, and the system was heated up to 80 °C. Then the solution was stirred and finally kept for 4 days at a constant temperature of 25 °C. The sample pH was controlled by changing the NaOH concentration.
General procedure: An acetonitrile mixture (15 ml) containing the long alkyl bromoalkane(15 mmol) or the potassium salt of chloroacetic acid(11.25 mmol) was placed in a semi-automated system EasyMax 102(Mettler Toledo) equipped with a 50 mL glass reactor, magneticstirring bar and ReactIR probe. After 5 min of stirring at 80 C, the appropriate tertiary amine (15 mmol) or dimethyldodecylamine(11.25 mmol) was quickly added. The reaction was carried out at 80 C and the optimal time of the reaction was determined byReactIR iC15 (Mettler Toledo) equipped with a MCT detector anda 9.5 mm AgX probe with a diamond tip. Data were sampled from2500 to 650 cm1 with 8 cm1 resolution and processed by iCIR 4.3software. Upon completion, the mixture was cooled to 20 C andthe solvent was removed by rotary evaporator under vacuum. Next,the obtained precursors were purified by washing repeatedly with acetone and dried under reduced pressure (5 mbar) at 60 C for24 h.
N,N-dimethyl-N-(4-methylpyridyl)-N-dodecylammonium chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
In acetonitrile at 20℃; for 24h;
3.2. Typical Procedure of Synthesis of N,N-Dimethyl-N-(4-methylpyridyl)-N-alkylammoniumChlorides P13-P18
General procedure: A mixture of 4-chloromethylpyridine (6, 1 g, 7.87 mmol) and an N,N-dimethylalkylamine(7.87 mmol) in CH3CN (10 mL) was stirred at room temperature for 24 h. Completion of reaction wascontrolled by TLC (CHCl3:MeOH 5:1). Then the solvent was evaporated under reduced pressure andthe residue was washed twice with diethyl ether. The crude dark brown product was purified byrecrystallization from acetone/acetonitrile (1:1).
22 Example 22: Formation of an Ammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS 328-50-7) and Ν,Ν-dimethyldodeclyamine (DiMeC12A, CAS 112-18-5) in a 1:1 Molar Ratio (referred to herein as AKG-mono(DiMeC12A)).
[0249] 2.922 g (0.02 moles) of a-ketoglutaric acid was dissolved in 12 mL of dry acetone. This solution was added dropwise with stirring over the course of 1-2 minutes to a separate solution of 4.268 g (0.02 moles) of N, N-dimethyldodecylamine in 6 mL of dry acetone. The mixture was shaken, but no visible indication of reaction was seen except that the combined solution warmed up to about 35 - 40° C. The mixture remained clear for a few minutes, but when shaken again, the entire mass instantly solidified into a solid white crystalline block. This solid was warmed up to 30 - 35° C to re-liquify the product so that entrapped acetone could be removed via a stream of nitrogen followed by treatment in a vacuum oven at room temperature. This gave a white, waxy solid in quantitative yield.
α-ketoglutaric acid di(N,N-dimethyldodecyl amine) salt[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
100%
In acetone at 35 - 40℃;
16 Example 16: Formation of a Diammonium Salt via the Reaction of a-Ketoglutaric Acid (CAS 328-50-7) and Ν,Ν-dimethyldodeclyamine (DiMeC12A, CAS 112-18-5) in a 1:2 Molar Ratio.
[0233] 1.461 g (0.01 moles) of a-ketoglutaric acid was dissolved in 6 mL of dry acetone. This solution was added dropwise with stirring over the course of 1-2 minutes to a separate solution of 4.268 g (0.02 moles) of N, N dimethyldodecylamine in 6 mL of dry acetone. No visible indication of reaction was seen except that the combined solution warmed up to about 35 - 40° C. The mixture was shaken briefly but vigorously, and cooled in a freezer for 30 minutes. Even when cold, still no precipitation of product occurred, but when the mixture was shaken again, the entire mass almost instantly solidified into a solid, white, waxy substance. This solid was warmed up to 30 - 35° C to re-liquify the product so that entrapped acetone could be removed via a stream of nitrogen followed by treatment in a vacuum oven at room temperature. This gave a white, waxy solid containing the diammonium salt (AKG- DiMeC12A salt).
With sodium iodide; In ethanol; at 65℃; for 45.0h;
With a thermometer,Add 100 parts by mass to the vessel of the stirring rod and the reflux condenser<strong>[13501-76-3]3-chloropropylmethyldiethoxysilane</strong>,203 parts by mass of N,N-dimethyldodecyl tertiary amine,130 parts by mass of absolute ethanol and 4.3 parts by mass of sodium iodide,The temperature was raised to 65 C for 45 hours, the anhydrous ethanol was distilled off, and the temperature was raised to 130 C.The pressure is reduced to -0.098 MPa or less, and the unreacted raw materials are distilled off.A quaternized methyldiethoxysilane is obtained.
N-(3-chloro-2-hydroxypropyl)trimethylammonium chloride[ No CAS ]
2-hydroxy-N<SUP>1</SUP>,N<SUP>1</SUP>,N<SUP>3</SUP>,N<SUP>3</SUP>-tetramethyl-N<SUP>3</SUP>-dodecylpropane-1,3-diammonium chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
83.7%
In ethanol; water at 80℃; for 5h;
Synthesis of N-Alkyl Bis-Quaternary Ammonium Salt Surfactants
Herein, the preparation of HPDDC was selected as an example to elaborate the synthetic procedure. The reactants were prepared by dissolving 0.10 mol of N,N-dimethyldodecylamine into 40 mL of ethanol and 0.10 mol of M into 10 mL of distilled water. Afterward, the asprepared reactants were mixed and added into a three necked flask, followed by being refluxed uniformly at 80 C for 5 h. After removing solvent, the obtained product was recrystallized using a mixture of ethanol and ethyl acetate(Vethanol:Vethyl acetate = 1:20) and being dried under vacuum. In this way, white-solid HPDDC powders can be produced, with a yield of 83.7%. Same procedure was applied to the synthesis of HPTDC and HPHDC by replacing N,N-dimethyldodecylamine with N,N-dimethyltetradecylamine,and N,N-dimethylhexadecylamine, respectively. The corresponding yields were 82.5% and 85.6%.
In water at 90℃; for 4h;
1; 2 Example 2
60% by mass of trimethylamine hydrochloride aqueous solution was poured into the kettle, and epichlorohydrin was added dropwise at a molar ratio of 1:0.9. The reaction was carried out at 40 ° C for 1 hour under stirring to obtain an intermediate N-(3-chloro 2-hydroxypropyl)-N,N,N-trimethylammonium chloride. Then, the temperature was raised to 90 ° C, and the dodecyl dimethyl tertiary amine with a molar ratio of trimethylamine hydrochloride of 1:0.9 was added to the above reaction system in one time, and the system pressure was raised to 0.3 Mpa for 4 hours, and diluted to The activity was 40% aqueous solution, and the reaction yield was 95.32% (based on the conversion of dodecyldimethylamine).
3-oxa-1,5-pentane-bis(N-dodecyl-N,N-dimethylammonium bromide)[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
98%
In neat (no solvent) at 20℃; for 2h;
12-O-12
The N-dodecyl-N,N-dimethylamine (10 g; 0.047 mol) was placed in a 100 ml round-bottom flask and bis(2-bromoethyl)ether (5.45g; 0.0235 mol) was added. Reaction was carried out without solvent, at room temperature, with stirring using a magnetic stirrer, until the reaction mixture solidified. After completion of the reaction crude product was crystallized in acetonitrile/methanol (10:1). The product was filtered and dried in an incubator (60°C) and over P4O10 in the vacuum desiccator. The yield of the reaction was >98%.
In neat (no solvent) at 20℃; for 0.2h; Green chemistry;
Synthesis of bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides
General procedure: Most of the bis(N-alkyl-N,N-dimethylethylammonium)ether dibromides, except for bis(N-octadecyl-N,N-dimethylethylammonium)ether dibromide, were synthesized analogously to the method described previously [26]; 1 equiv of bis(2-bromoethyl)ether was mixed with 2 equiv of suitable N-alkyl-N,N-dimethylamine ( N-butyl-N,N-dimethylamine for 4-O-4; N-hexyl-N,N-dimethylamine for 6-O-6; N-octyl-N,N-dimethylamine for 8-O-8; N-decyl-N,N-dimethylamine for 10-O-10; N-docecyl-N,N-dimethylamine for 12-O-12; N-tetradecyl-N,N-dimethylamine for 14-O-14; and N-hexadecyl-N,N-dimethylamine for 16-O-16). The reactions were carried out without solvent, at room temperature, with stirring using a magnetic stirrer until the reaction mixture solidified (approx. 2 h). The crude products were crystallized from acetonitrile with a small addition of methanol and dried over P4O10 in a dryer. Bis(N-octadecyl-N,N-dimethylethylammonium)ether dibromide was obtained according to Ref.[27]; 1 equiv of bis(2-bromoethyl)ether and 2 equiv of N-octadecyl-N,N-dimethylamine was refluxed in acetonitrile until the reaction mixture solidified. Then, the crude product was crystallized from a mixture of acetonitrile:methanol (10:1) and dried over P4O10 in a dryer. The general formula and abbreviations for the alkylammonium gemini surfactants obtained are presented in Fig.1.
In acetonitrile at 82℃; for 24h; Inert atmosphere;
1.3
(3) Under a nitrogen atmosphere, 1.2 g (3.0 mmol) of Intermediate B was placed in a 100 ml three-necked flask.1.07 g (5 mmol) of N,N-dimethyldodecanamine and 50 ml of acetonitrile were charged to the reactor using a constant pressure dropping funnel. Reflux at 82 ° C for 24 h.After the reaction is completed, a yellow turbid liquid is obtained, which is evaporated to dryness under reduced pressure and then applied to silica gel column chromatography(Dichloromethane and methanol) gave white product 1.35 g, yield 79.4%.
N,N-dimethyl(4-chlorobutyl)dodecyl ammonium chloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
95%
With tetrabutyl-ammonium chloride In ethanol for 9h; Reflux;
3.1 Example 3
The method for synthesizing the ionic liquid-based Gemini cationic surfactant of the present embodiment has the following steps: (1) 19.05 g (0.15 mol) of 1,4-dichlorobutane,20 g of ethanol was added to a four-neck round bottom flask, and the mixture was heated to boiling under stirring.Add 1.5g of tetrabutylammonium chloride,10.65 g (0.05 mol) of N,N-dimethyldodecyl tertiary amine was added dropwise to maintain the reflux temperature.After stirring the reaction for 9 hours, ethanol was distilled off under reduced pressure, and the solid was washed three times with chloroform.The filter cake is dried under vacuum at 60 ° C for 6 hours to obtain an intermediate.N,N-dimethyl(1-chlorobutyl)dodecyl ammonium chloride, yield 95%;
N,N-dimethyl(3-bromopropyl)dodecyl ammonium bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90.5%
With tetrabutylammomium bromide In methanol for 8h; Reflux;
1.1 Example 1
The synthesis method of the ionic liquid-based Gemini cationic surfactant of this embodiment is as follows: (1) 40.38 g (0.2 mol) of 1,3-dibromopropane and 20 g of methanol were added to a four-neck round bottom flask.The mixture was heated to boiling with stirring, and 1 g of tetrabutylammonium bromide was added.10.67 g (0.05 mol) of N,N-dimethyldodecyl tertiary amine was added dropwise.Maintain the reflux temperature,After stirring the reaction for 8 hours, methanol was distilled off under reduced pressure, and the solid was washed three times with ethyl acetate.The filter cake was dried under vacuum at 50 ° C for 10 hours to obtain an intermediate.N,N-dimethyl(1-bromopropyl)dodecyl ammonium bromide, yield 90.5%;
N,N-dimethyl(3-iodopropyl)dodecyl ammonium iodide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
96%
With tetra-(n-butyl)ammonium iodide; In ethanol; for 8h;Reflux;
The synthesis method of the ionic liquid-based Gemini cationic surfactant of this embodiment is as follows:(1) 59.78 g (0.202 mol) of 1,3-diiodopropane and 20 g of ethanol were placed in a four-neck round bottom flask, and the mixture was heated to boiling with stirring, and 1 g of tetrabutylammonium iodide was added thereto, and 14.23 g (0.0668 mol) was added dropwise. N,N-dimethyldodecyl tertiary amine, maintainedAfter refluxing for 8 hours, the ethanol was distilled off under reduced pressure, the solid was washed three times with chloroform, and the cake was vacuum dried at 60 C for 6 hours to obtain an intermediate.N,N-dimethyl(1-iodopropyl)dodecyl ammonium iodide, yield 96%;
With sodium hydroxide In ethanol; water at 100℃; for 24h;
16 Example 16
Method in reference (J.Am.Chem.Soc.2001,123,5614-561.):Dissolving dimethylamine hydrochloride (3.74g, 45.9mmol) in 50mL of ethanol-water mixed solvent (v / v = 95: 5),After adding sodium hydroxide (2.20 g, 53.4 mmol) to the system and dissolving with stirring,Add 1-bromododecane (3.80g, 3.66mL, 15.3mmol) under reflux at 100 ° C for 24h;After removing the solvent by vacuum concentration, add 40ml of a 10% sodium hydroxide solution and stir,The product was then extracted three times with 20 mL of dichloromethane, and after concentration in vacuo, compound 24 was obtained as a pale red liquid (2.59 g, 80.9%).
Naph-MS: 11.20 g (51.0 mmol) N, N-dimethyl long-chain alkyl tertiaryamine and 8.80 g (50.0 mmol) chloromethyl naphthalene wasadded to a 250 mL 3-necked flask with 75mL 1,4-dioxane. The mixturewas stirred at 70 °C for 10 h. After cooling to roomtemperature, the solventwasremoved under reduced pressure and give light yellow blockysolid. These light yellow blocky solid was washed by cyclohexane(3 × 10 mL), and dried under vacuum to get 8.50 g light yellow waxysolid (Naph-MS), yield 87%.
(4R)-N,N-dimethyl-N-[4-(prop-1-en-2-yl)cyclohex-1-en-1-yl]methyl}dodecylammonium bromide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
90%
In benzene at 20℃; Reflux;
General Procedure for Preparation of Quaternary AmmoniumBromides 4a-e, 7a-e, 10a-e
General procedure: Bromide 2 (1.0 mmol) was placed in the flask, thenanhydrous benzene and tertiary amine (1.1-1.3 mmol)were introduced. The reaction was carried out at reflux for4-6 hours and stirred overnight at room temperature. Thereaction mixture was evaporated and after dissolving theresidue in a small amount of benzene the product was precipitatedwith ethyl ether. The operation was repeated dependingon the derivative from two to three times. Yieldsranged from 70% for reactions with long chain amines upto 98% for shorter chain amines.
5,8-bis(chloromethyl)-2-ethyl-4H-[1,3]dioxino[4,5-c]pyridinium chloride[ No CAS ]
5,8-bis(methylene(N,N-dimethyl-N-dodecylammonium))-2-ethyl-4H-[1,3]dioxino[4,5-c]pyridinium dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
Stage #1: 5,8-bis(chloromethyl)-2-ethyl-4H-[1,3]dioxino[4,5-c]pyridinium chloride With water; sodium hydrogencarbonate
Stage #2: N,N-dimethylaminododecane In ethanol at 70℃; for 8h;
1.7 Phase 7: Preparation of 5,8-(Bis (methylene (N, N-dimethyl-N-dodecylammonium))-2-ethyl-4H-[1,3]dioxino [4,5-c] pyridinium dichloride (I)
To a solution of 1.1 g (13.1 mmol) of sodium bicarbonate in 40 ml of water, 3.8 g (12.7 mmol) of compound 6 was added while stirring. The resulting precipitate was filtered off and dried in vacuo. The resulting 2.9 g (11.1 mmol) of product (88% yield) were dissolved in 50 ml of ethanol and 5.98 ml (22.2 mmol) of N, N-dimethyldodecylamine were added. The reaction mixture was stirred at 70° C. for 8 hours. The solvent was distilled off in a vacuum. The resulting precipitation was boiled in 120 ml of acetone. After cooling to room temperature, the precipitation was filtered off and dried in vacuo. Yield is 5.64 g (74%), white crystalline substance.NMR spectrum 1H (400 MHz, CDCl3) δ, ppm: 0.84 t (6H, 3JHH=6.7 Hz, 2CH3C11H22), 1.00 t (3H, 3JH-H=7.5 Hz, CH3CH2), 1.22-1.33 m (32H, 16CH2), 1.70-1.84 m (6H, 3CH2), 2.96 m (2H, CH2), 3.29-3.32 m (12H, 4CH3N+), 3.50-3.83 m (4H, 2CH2N+), 4.69, 4.74 (AB-system, 2H, 2JHH=-13.6 Hz, CH2), 5.10, 5.55 (AB-system, 2H, 2JHH=-16.7 Hz, CH2), 5.11, 5.21 (AB-system, 2H, 2JHH=-13.6 Hz, CH2), 8.60 s (1H, CHpyr).NMR spectrum 13C (100 MHz, CDCl3) δ, ppm: 8.01 s (CH3), 14.21 s (CH3), 22.77 s (CH3), 23.18 s (CH2), 26.46 s (CH2), 27.57 s (CH2), 29.43 s (CH3), 29.46 s (CH2), 29.53 s (CH2), 29.62 s (CH2), 29.70 (s, CH2), 31.99 s (CH2), 49.60 s (CH3N+), 49.76 s (CH3N+), 51.11 s (CH3N+), 51.34 s (CH3N+), 61.94 s (CH2), s 62.26 (CH2), 65.60 s (CH2), 65.66 s (CH2N+), 66.34 s (CH2N+), 102.04 s (C(CH3)2), 122.92 s (Cpyr), 134.60 s (Cpyr), 136.87 s (Cpyr), 146.54 s (Cpyr), 150.88 s (Cpyr).
5,8-bis(chloromethyl)-2-ethyl-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis(methylene(N,N-dimethyl-N-dodecylammonium))-2-ethyl-4H-[1,3]dioxino[4,5-c]pyridinium dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
2-(tert-butyl)-5,8-bis(chloromethyl)-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-(tert-butyl)-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
2-(sec-butyl)-5,8-bis(chloromethyl)-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-(sec-butyl)-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
60%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-pentyl-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-pentyl-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-(pentan-2-yl)-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-(pentan-2-yl)-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-hexyl-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-hexyl-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-heptyl-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-heptyl-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
78%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-(heptan-3-yl)-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-(heptan-3-yl)-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
62%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-octyl-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-octyl-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
5,8-bis(chloromethyl)-2-(undecan-2-yl)-4H-[1,3]dioxino[4,5-c]pyridine[ No CAS ]
5,8-bis((N,N-dimethyl-N-(dodecyl)ammonio)methyl)-2-(undecan-2-yl)-4H-[1,3]dioxino[4,5-c]pyridine dichloride[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
In ethanol at 70℃; for 5h;
General procedure for preparation of quaternary ammonium salts 5a8-5r18
General procedure: Amine (2 equiv) was added to a solution of compound 4a-4r (1 equiv) in 10 ml of ethanol. The reaction mixture was heated at 70 °C for 5h, then the solvent was evaporated under reduced pressure. The oily residue was refluxed in acetone for 1h and the crystalline precipitate was filtered and dried under reduced pressure.
Stage #1: N,N-dimethylaminododecane With hydrogenchloride In ethanol; water at 20℃; for 0.0833333h;
Stage #2: epichlorohydrin In ethanol; water at 50℃; for 6h;
2 Embodiment two:
First dissolve 100 mmol of dodecyl dimethyl tertiary amine in 100 mL of ethanol, then add 100 mmol of hydrogen chloride to the round-bottom flask, and stir at room temperature for 5 minutes to completely dissolve the hydrochloric acid in the solution. Then, 100 mmol of epichlorohydrin was added to the flask, and the temperature was raised to 50° C., and the reaction was carried out for 6 hours. After the completion of the reaction, the ethanol and epichlorohydrin were removed by rotary evaporation, and finally a light yellow viscous paste was obtained, which was placed in a drying flask for later use, denoted as HYZ-12, and the yield was 85%.
2.4 Preparation of (EtO)3Si(CH2)3N+(CH3)2CnH2n+1I- (n=8, 12, 16)
General procedure: The whole reaction was carried out under a nitrogen atmosphere. After 2 mL of anhydrous toluene was transferred to a 15 mL high-pressure glass tube, 5 mmol N(CH3)2CnH2n+1(n = 8, 12, 16), 5.5 mmol (EtO)3Si(CH2)3I were sequentially added. After reacting at 120 °C for 36 h, it was naturally cooled to room temperature. 2 mL of dichloromethane was added to dissolve the product. 60 mL n-pentane was added dropwise to extract and remove toluene. After low-speed centrifugation, the bottom layer was a white oily liquid (n=8). After removing the dichloromethane, a dark red oily liquid was obtained. In addition, the crude product of the ligand precursor (n=12, 16) was directly rotary evaporated to remove toluene to get a dark yellow oily liquid (n=12) and a light yellow oily liquid (n=16), respectively
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