Reductive Methylation of Homogeneous Primary β-Lauryl/myristyl 7/3 Polyethyleneoxy n = 3–18 Ethylamines under Phase-Transfer Catalysis Conditions
Abstract
:1. Introduction
2. Results and Discussions
3. Materials and Methods
3.1. Chemicals
3.2. Synthesis and Characterization of Reference Chemicals
3.3. Chemical and Physico-Chemical Characterization of Homogeneous Lauryl/myristyl Alcohols 7/3 as such and Polyethoxylated n = 3–18
3.4. The Overall Scheme of Synthesis Reactions of Homogeneous LM(EO)nAT from Homogeneous LM(EO)nOH
3.5. Synthesis and Characterization of Homogeneous LM(EO)nAT under Conditions of Phase-Transfer Catalysis
4. Conclusions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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No. | Degree of Oligomerization (n) | Reductive Methylation Yield (%) |
---|---|---|
1 | 3 | 81.32 |
2 | 6 | 86.42 |
3 | 9 | 90.17 |
4 | 12 | 92.36 |
5 | 18 | 95.02 |
No. | Degree of Oligomerization (n) | Reaction Time (Minute) | Reductive Methylation Yield (%) |
---|---|---|---|
1 | 3 | 10 | 31.22 |
2 | 30 | 47.15 | |
3 | 50 | 62.51 | |
4 | 90 | 80.83 | |
5 | 18 | 10 | 49.02 |
6 | 30 | 60.61 | |
7 | 50 | 77.43 | |
8 | 90 | 94.61 |
No. | Degree of Oligomerization (n) | Molar Ratio Formic Aldehyde /LM(EO)3;18AP | Reductive Methylation Yield (%) |
---|---|---|---|
1 | 3 | 1.1/1 | 59.43 |
2 | 1.3/1 | 62.54 | |
3 | 1.7/1 | 69.61 | |
4 | 2.0/1 | 76.32 | |
5 | 2.2/1 | 90.52 | |
6 | 2.5/1 | 99.14 | |
7 | 18 | 1.1/1 | 74.32 |
8 | 1.3/1 | 77.13 | |
9 | 1.7/1 | 92.20 | |
10 | 2.0/1 | 94.03 | |
11 | 2.2/1 | 97.74 | |
12 | 2.5/1 | 99.25 |
No. | Homogeneous Degree of Oligomerization, n, of Ethylene Oxide in the Structure a CTF1 | Critical Micellar Concentration (×10–5 mol/L) |
---|---|---|
1 | 3 | 1.31 |
2 | 6 | 1.11 |
3 | 9 | 0.82 |
4 | 12 | 0.53 |
5 | 18 | 0.40 |
No. | Homogeneous Degree of Oligomerization, n, of Ethylene Oxide in the Structure LM(EO)nAT | Critical Micellar Concentration (×10–5 mol/L) |
---|---|---|
1 | 3 | 1.43 |
2 | 6 | 1.22 |
3 | 9 | 0.94 |
4 | 12 | 0.64 |
5 | 18 | 0.49 |
Alcohol | Physico-Chemical Characteristics | ||||
---|---|---|---|---|---|
Density (g/cm3)/Temperature (°C) | Solidification Range, (°C) | Clouding Point [36,37], (°C) | Hydroxyl Value [38,39], (mg KOH/g) | Ethylene Oxide Content [40,41], (%) | |
Lauryl/myristyl alcohol | 0.830/25 | 33–35 | - | - | - |
Polyethoxylated lauryl/myristyl alcohol (n = 3) | 0.891/70 | - | - | 180.41 | 42.52 |
Polyethoxylated lauryl/myristyl alcohol (n = 6) | 0.933/70 | 20–23 | 46–50 | 126.58 | 59.67 |
Polyethoxylated lauryl/myristyl alcohol (n = 9) | 0.943/70 | 26–28 | 58–67 | 97.49 | 68.94 |
Polyethoxylated lauryl/myristyl alcohol (n = 12) | 0.966/70 | 31–34 | 87–96 | 79.27 | 74.74 |
Polyethoxylated lauryl/myristyl alcohol (n = 16) | 0.975/70 | 36–38 | >100 | 63.45 | 79.78 |
Polyethoxylated lauryl/myristyl alcohol (n = 18) | 0.984/70 | 38–40 | >100 | 52.91 | 83.14 |
No. | Primary Polyether Amine | Nitrogen Content [42,43], (%) | Ethylene Oxide Content [40,41], (%) | ||
---|---|---|---|---|---|
Experimental | Theoretical | Experimental | Theoretical | ||
1 | β-lauryl/myristyl 7/3 oxy-ethylamine | 5.884 | 3.897 | - | - |
2 | β-lauryl/myristyl 7/3 polyethyleneoxy n = 3 ethylamine | 3.770 | 3.790 | 35.545 | 35.733 |
3 | β-lauryl/myristyl 7/3 polyethyleneoxy n = 6 ethylamine | 2.781 | 2.792 | 52.449 | 52.652 |
4 | β- lauryl/myristyl 7/3 polyethyleneoxy n = 9 ethylamine | 2.201 | 2.210 | 62.268 | 62.520 |
5 | β-lauryl/myristyl 7/3 polyethyleneoxy n = 12 ethylamine | 1.818 | 1.829 | 68.594 | 68.983 |
6 | β lauryl/myristyl 7/3 polyethyleneoxy n = 16 ethylamine | 1.482 | 1.487 | 74.546 | 74.782 |
7 | β-lauryl/myristyl 7/3 polyethyleneoxy n = 18 ethylamine | 1.250 | 1.253 | 78.582 | 78.757 |
No. | Symbol | Ethylene Oxide Content [40,41], (%) | Hydroxyl Value [38,39], (mg KOH/g) | Refractive Index, | |||
---|---|---|---|---|---|---|---|
Determined | Calculated | Determined | Calculated | Determined | Calculated | ||
1 | PEG—3 | 87.204 | 88.000 | 370.294 | 373.330 | - | - |
2 | PEG—6 | 92.480 | 93.617 | 106.168 | 198.501 | 1.4523 | 1.4520 |
3 | PEG—9 | 94.772 | 95.650 | 130.024 | 135.256 | 1.4593 | 1.4591 |
4 | PEG—12 | 95.886 | 96.703 | 101.698 | 102.564 | 1.4606 | 1.4608 |
5 | PEG—18 | 97.080 | 97.770 | 68.639 | 69.135 | 1.4626 | 1.4628 |
No. | Homogeneous Degree of Oligomerization (n) | EOn—Ac | EOn—2Ac | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
Ethylene Oxide Content [40,41], (%) | Hydroxyl Value [38,39], (mg KOH/g) | Purity (%) | Ethylene Oxide Content [40,41], (%) | Hydroxyl Value [38,39], (mg KOH/g) | Purity (%) | ||||||||
Detd. | Calcd. | Detd. | Calcd. | Detd. | Calcd. | Detd. | Calcd. | Detd. | Calcd. | Detd. | Calcd. | ||
1 | 3 | 68.56 | 68.75 | 290.88 | 291.67 | 99.73 | 55.78 | 56.41 | 1.782 | - | 98.90 | 3 | 68.56 |
2 | 6 | 81.11 | 81.48 | 172.05 | 172.84 | 99.54 | 70.32 | 71.93 | 1.803 | - | 97.76 | 6 | 81.11 |
3 | 9 | 86.21 | 86.84 | 121.93 | 122.81 | 99.28 | 79.17 | 79.52 | 1.647 | - | 99.56 | 9 | 86.21 |
4 | 18 | 89.05 | 89.79 | 94.45 | 95.24 | 99.17 | 83.54 | 83.81 | 1.025 | - | 99.68 | 12 | 89.05 |
No. | Homogeneous Degree of Oligomerization (n) | (EO)n—Na | (EO)n—2Na | ||
---|---|---|---|---|---|
Purity (%) | Purity (%) | ||||
Determined 1 | Calculated | Determined 1 | Calculated | ||
1 | 3 | 99.04 | 99.18 | 99.18 | 99.79 |
2 | 6 | 99.37 | 99.86 | 99.03 | 99.77 |
3 | 9 | 99.43 | 99.88 | 98.99 | 99.83 |
4 | 18 | 99.78 | 99.53 | 99.36 | 99.88 |
No. | Homogeneous Tertiary Polyether Amine | Ethylene Oxide Content [40,41], (%) | Nitrogen Content [42,43], (%) | ||
---|---|---|---|---|---|
Experimental | Theoretical | Experimental | Theoretical | ||
1 | N,N-dimethyl-N-β-lauryl/myristyl 7/3 oxy ethylamine | - | - | 5.247 | 5.275 |
2 | N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 3 ethylamine | 33.061 | 33.216 | 3.505 | 3.522 |
3 | N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 6 ethylamine | 46.619 | 49.867 | 2.631 | 2.644 |
4 | N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 9 ethylamine | 59.704 | 59.873 | 2.111 | 2.117 |
5 | N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 12 ethylamine | 66.294 | 66.549 | 1.758 | 1.765 |
6 | N,N-dimethyl-N-β-lauryl/myristyl 7/3 polyethyleneoxy n = 18 ethylamine | 76.270 | 76.829 | 1.213 | 1.222 |
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Jianu, C. Reductive Methylation of Homogeneous Primary β-Lauryl/myristyl 7/3 Polyethyleneoxy n = 3–18 Ethylamines under Phase-Transfer Catalysis Conditions. Molecules 2021, 26, 4612. https://doi.org/10.3390/molecules26154612
Jianu C. Reductive Methylation of Homogeneous Primary β-Lauryl/myristyl 7/3 Polyethyleneoxy n = 3–18 Ethylamines under Phase-Transfer Catalysis Conditions. Molecules. 2021; 26(15):4612. https://doi.org/10.3390/molecules26154612
Chicago/Turabian StyleJianu, Călin. 2021. "Reductive Methylation of Homogeneous Primary β-Lauryl/myristyl 7/3 Polyethyleneoxy n = 3–18 Ethylamines under Phase-Transfer Catalysis Conditions" Molecules 26, no. 15: 4612. https://doi.org/10.3390/molecules26154612