haiii i havent seen this posted here yet. i stole it from the vespiary, so heres the original thread :3
(i added numbers to make things easier, lmk if i need to fix anything)
There are some very promising, unexplored synthesis routes from alpha-methyl-3,4-methylenedioxypheny-propionamide
to MDA and MDMA.
1. J . Chem. Tech. Biotechnol. 1994, 59, 271-277
General procedure for preparation of carbamates:
Fatty amide (0.2 mol) was dissolved in methanol (250 cm3)
with stirring. To it, a freshly prepared aqueous solution
of NaOCl (0.21 mol, 125 cm3) was added immediately
with good stirring. Additional methanol (100 cm3) was
added to the reaction mixture in the case of undecylamide
and lauramide. The temperature rose to about 52-55°C
within 30 min and the solution was then refluxed for 2 h.
Methanol (200 cm3) was recovered from the reaction
mixture by distillation. On cooling the reaction mixture
was diluted with water (200 cm3) and extracted with
dichloromethane (3 x 50 cm3). The combined extracts
were washed with water and dried over Na,S04.
Dichloromethane was recovered by distillation, leaving
carbamate as the residue.
2. Basic hydrolysis of carbamate to amine in aqueous ethanol; p-(trans-4-Heptylcyclohexyl) aniline
cssp.chemspider.com
Procedure:
To a 100ml round bottom three neck flask, equipped with heating mantle, mechanical stirrer, water condenser and nitrogen inlet was charged 32ml of 200 proof ethanol, 8 ml of deionized water and 0.512g (1.55 mmol) of methyl- (p-trans-heptylcyclohexyl)carbamate. The mixture was stirred until homogeneous. 10g of potassium hydroxide pellets were then added and the mixture stirred until all of the pellets has dissolved. The solution was refluxed under nitrogen for 24 hours and then allowed to cool to room temperature. The reaction mixture was transferred to a 100ml round bottom flask and the ethanol removed on a rotory evaporator (water bath, bath temperature ~ 60?, water aspirator pressure). The aqueous residue was cooled to room temperature, transferred to a 100 ml separatory funnel, and extracted three times with 10ml ether portions. The combined ether extracts were dried for 2 hours over 2g anhydrous sodium sulfate and the ether solution decanted off to a 100 ml round bottom flask. The sodium sulfate residue was shaken with 10 additional ml of ether which was decanted and combined with the earlier extracts. The ether was removed on a rotory evaporator (water bath, bath temperature ~ 60?), yielding 0.348g (88%) of essentially pure amine, which solidified on standing at room temperature. The material may be further purified by distillation on a short path Kugelrohr apparatus (0.1mm, pressure, oil bath temperature ~140? ) to yield an analytically pure sample.
3. MDMA
General procedure for N-alkylation of carbamates:
A mixture of carbamate (005 rnol), toluene (100 cm3),
powdered NaOH (0.2 mol), anhydrous K,C03 (0.05 mol)
and tetrabutylammonium hydrogen sulfate (0.0025 mol)
was stirred at room temperature for 1 h. During stirring,
a gelatinous mass was formed. Dimethyl sulfate (0.06 mol)
was added to the stirred mass a t 30-35°C over a period
of 30min. The course of the reaction was followed by
TLC. The reaction mixture was stirred for 4 h to obtain
a clear solution. Inorganics were filtered off and washed
with toluene (2 x 20cm3). The combined filtrate and
washings were washed with HCI (2 N, 3 x 50 cm3), water
(2 x 50 cm3) and dried over anhydrous Na,S04. Concentration
of the solvent yielded the products.
4. Basic hydrolysis of N-methyl carbamate should yield MDMA.
Preparation of Methyl N-Substituted Carbamates from Amides through N-Chloroamides
An efficient modification of the Hofmann rearrangement:
synthesis of methyl carbamates
Tetrahedron Letters 48 (2007) 531–533
2.1. Typical experimental procedure for the synthesis of
methyl carbamate
To a solution of benzamide (1 mmol) in methanol (7 ml),
KF/Al2O3 (2 g, 40% by weight) and NaOCl (3 ml of a
4% aqueous solution) were added and the mixture was
refluxed for 30 min. After cooling the reaction mixture
to room temperature, the solid base was filtered.
Methanol was then removed by rotary evaporation
and the residue was dissolved in EtOAc (20 ml). The
EtOAc layer was washed with water (10 ml · 3), dried
over anhydrous sodium sulfate and concentrated under
reduced pressure to give a crude product which was
purified by crystallization using petroleum ether.
5. Cleavage of carbamates
SYNTHESIS 2008, No. 11, pp 1679–1681x.x.
Synthesis of 4-Methylbenzylamine Hydrochloride (3a); Typical
Procedure:
4-Methylbenzaldehyde (24 mg, 0.2 mmol), methyl carbamate (30
mg, 0.4 mmol), TFA (91 mg, 0.8 mmol) and TBDMSH (114 mg,
0.8 mmol) were dissolved in MeCN (4.0 mL) and heated to 150 °C
for 15 min in a Smith Synthesizer™ microwave apparatus. The
mixture was concentrated in vacuo and the residue was dissolved in
a mixture of THF, MeOH and 2M LiOH (1:1:1, 4 mL) and heated
at 120 °C for 10 min in a Smith Synthesizer™. EtOAc (4 mL) and
1M NaOH (4 mL) were added and the phases were separated. The
organic phase was extracted with 1M HCl (2 × 4 mL) and the aqueous
extract was evaporated to afford 4-methylbenzylamine as its hydrochloride
salt (28 mg, 89%). The purity of this material was at
least 99% as determined by LC-MS.
someone in the replies suggested #3, i have a PDF that someone else in the replies said was geared more towards "the average bee" but for some reason i cant post it ^^;
(i added numbers to make things easier, lmk if i need to fix anything)
There are some very promising, unexplored synthesis routes from alpha-methyl-3,4-methylenedioxypheny-propionamide
to MDA and MDMA.
1. J . Chem. Tech. Biotechnol. 1994, 59, 271-277
General procedure for preparation of carbamates:
Fatty amide (0.2 mol) was dissolved in methanol (250 cm3)
with stirring. To it, a freshly prepared aqueous solution
of NaOCl (0.21 mol, 125 cm3) was added immediately
with good stirring. Additional methanol (100 cm3) was
added to the reaction mixture in the case of undecylamide
and lauramide. The temperature rose to about 52-55°C
within 30 min and the solution was then refluxed for 2 h.
Methanol (200 cm3) was recovered from the reaction
mixture by distillation. On cooling the reaction mixture
was diluted with water (200 cm3) and extracted with
dichloromethane (3 x 50 cm3). The combined extracts
were washed with water and dried over Na,S04.
Dichloromethane was recovered by distillation, leaving
carbamate as the residue.
2. Basic hydrolysis of carbamate to amine in aqueous ethanol; p-(trans-4-Heptylcyclohexyl) aniline
ChemSpider SyntheticPages | Basic hydrolysis of carbamate to amine in aqueous ethanol
Chemicals used, procedure, author comments, data and references for: Basic hydrolysis of carbamate to amine in aqueous ethanol.
cssp.chemspider.comProcedure:
To a 100ml round bottom three neck flask, equipped with heating mantle, mechanical stirrer, water condenser and nitrogen inlet was charged 32ml of 200 proof ethanol, 8 ml of deionized water and 0.512g (1.55 mmol) of methyl- (p-trans-heptylcyclohexyl)carbamate. The mixture was stirred until homogeneous. 10g of potassium hydroxide pellets were then added and the mixture stirred until all of the pellets has dissolved. The solution was refluxed under nitrogen for 24 hours and then allowed to cool to room temperature. The reaction mixture was transferred to a 100ml round bottom flask and the ethanol removed on a rotory evaporator (water bath, bath temperature ~ 60?, water aspirator pressure). The aqueous residue was cooled to room temperature, transferred to a 100 ml separatory funnel, and extracted three times with 10ml ether portions. The combined ether extracts were dried for 2 hours over 2g anhydrous sodium sulfate and the ether solution decanted off to a 100 ml round bottom flask. The sodium sulfate residue was shaken with 10 additional ml of ether which was decanted and combined with the earlier extracts. The ether was removed on a rotory evaporator (water bath, bath temperature ~ 60?), yielding 0.348g (88%) of essentially pure amine, which solidified on standing at room temperature. The material may be further purified by distillation on a short path Kugelrohr apparatus (0.1mm, pressure, oil bath temperature ~140? ) to yield an analytically pure sample.
3. MDMA
General procedure for N-alkylation of carbamates:
A mixture of carbamate (005 rnol), toluene (100 cm3),
powdered NaOH (0.2 mol), anhydrous K,C03 (0.05 mol)
and tetrabutylammonium hydrogen sulfate (0.0025 mol)
was stirred at room temperature for 1 h. During stirring,
a gelatinous mass was formed. Dimethyl sulfate (0.06 mol)
was added to the stirred mass a t 30-35°C over a period
of 30min. The course of the reaction was followed by
TLC. The reaction mixture was stirred for 4 h to obtain
a clear solution. Inorganics were filtered off and washed
with toluene (2 x 20cm3). The combined filtrate and
washings were washed with HCI (2 N, 3 x 50 cm3), water
(2 x 50 cm3) and dried over anhydrous Na,S04. Concentration
of the solvent yielded the products.
4. Basic hydrolysis of N-methyl carbamate should yield MDMA.
Preparation of Methyl N-Substituted Carbamates from Amides through N-Chloroamides
http://www.chembbs.com.cn/bbs/file/userfiles/upload/2009092402202058.pdf
An efficient modification of the Hofmann rearrangement:
synthesis of methyl carbamates
Tetrahedron Letters 48 (2007) 531–533
2.1. Typical experimental procedure for the synthesis of
methyl carbamate
To a solution of benzamide (1 mmol) in methanol (7 ml),
KF/Al2O3 (2 g, 40% by weight) and NaOCl (3 ml of a
4% aqueous solution) were added and the mixture was
refluxed for 30 min. After cooling the reaction mixture
to room temperature, the solid base was filtered.
Methanol was then removed by rotary evaporation
and the residue was dissolved in EtOAc (20 ml). The
EtOAc layer was washed with water (10 ml · 3), dried
over anhydrous sodium sulfate and concentrated under
reduced pressure to give a crude product which was
purified by crystallization using petroleum ether.
5. Cleavage of carbamates
SYNTHESIS 2008, No. 11, pp 1679–1681x.x.
Synthesis of 4-Methylbenzylamine Hydrochloride (3a); Typical
Procedure:
4-Methylbenzaldehyde (24 mg, 0.2 mmol), methyl carbamate (30
mg, 0.4 mmol), TFA (91 mg, 0.8 mmol) and TBDMSH (114 mg,
0.8 mmol) were dissolved in MeCN (4.0 mL) and heated to 150 °C
for 15 min in a Smith Synthesizer™ microwave apparatus. The
mixture was concentrated in vacuo and the residue was dissolved in
a mixture of THF, MeOH and 2M LiOH (1:1:1, 4 mL) and heated
at 120 °C for 10 min in a Smith Synthesizer™. EtOAc (4 mL) and
1M NaOH (4 mL) were added and the phases were separated. The
organic phase was extracted with 1M HCl (2 × 4 mL) and the aqueous
extract was evaporated to afford 4-methylbenzylamine as its hydrochloride
salt (28 mg, 89%). The purity of this material was at
least 99% as determined by LC-MS.
someone in the replies suggested #3, i have a PDF that someone else in the replies said was geared more towards "the average bee" but for some reason i cant post it ^^;