Author Topic: Methylone synthesis  (Read 4281 times)

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Chicken

  • Guest
Methylone synthesis
« on: September 26, 2002, 09:16:00 PM »
Do any bees know where a synthesis might be found for methylone, 2-methylamino-1-(3,4-methylenedioxyphenyl)propan-1-one.  There are some journal entries regarding it's effects which are, in thses articles it states that the methylone was synthed, but does not indicate what the synthesis proceedure is.  There alslo are several reports for usage on erowid at 

Inhibition of Plasma Membrane Monoamine Transporters by b-Ketoamphetamines,
Cozzi NV, Sievert MK, Shulgin AT, Jacob Peyton III, Ruoho AE
Eur. J. Pharmacol, 1999; 381:63-69

Post 493183 (missing)

(Rhodium: "Methcathinone & Methylone Pharmacology", General Discourse)

 
Methcathinone and 2-methylamino-1-(3,4-methylenedioxyphenyl)propan-1-one (methylone) selectively inhibit plasma membrane catecholaminereuptake transporters,
Cozzi NV, Sievert MK, Shulgin AT, Jacob Peyton III, Ruoho AE
Soc. Neurosci. Abs, 1998; 24: 381.8

Methcathinone (MCAT) and 2-methylamino-1-(3,4-methylenedioxyphenyl)propan-1-one (MDMCAT) inhibit [3H]serotonin uptake into human platelets,
Cozzi NV, Shulgin AT, Ruoho AE
Amer. Chem. Soc. Div. Med. Chem. Abs., 1998; 215: 152


Rhodium

  • Guest
Methylone
« Reply #1 on: September 26, 2002, 09:57:00 PM »
3,4-Methylenedioxybenzene + Propionic acid + Polyphosphoric acid -> 3,4-Methylenedioxypropiophenone

3,4-Methylenedioxypropiophenone + N-Bromo-succinimide -> alpha-bromo-3,4-Methylenedioxypropiophenone

alpha-bromo-3,4-Methylenedioxypropiophenone + Methylamine -> Methylone

PrimoPyro

  • Guest
Rhodium
« Reply #2 on: September 26, 2002, 10:20:00 PM »
Please tell me you can do the same reaction with formic acid, making piperonal.

Will perform sexual favors for females in exchange for 1,2-dimethylaziridine. PM for details.

Rhodium

  • Guest
Here is a reference for the reaction
« Reply #3 on: September 26, 2002, 10:37:00 PM »
Here is a reference for the reaction:

https://www.thevespiary.org/rhodium/Rhodium/chemistry/acetophenones.html



I have never heard of the reaction (which essentially is a FC acylation with PPA as the lewis acid) being used with formic acid. There is nothing that would stop any formed piperonal from acylating unreacted benzodioxole, so I guess your suggestion would be a dead end...

The following is a rather old Methylone patent:

Patent US3523954


Osmium

  • Guest
Formic + strong drying agent -----> CO + CO2
« Reply #4 on: September 26, 2002, 10:39:00 PM »
Formic + strong drying agent -----> CO + CO2

I'm not fat just horizontally disproportionate.

Antoncho

  • Guest
My ten cents
« Reply #5 on: September 28, 2002, 08:39:00 AM »
1st, as for HCOOH formylations - Primo, believe me, this IS a dead end, i've done once quite a thorough search on this and found nihil - there was one exciting article that Lugh sent me, but it turned out pretty discouraging as well.


2nd, AFAIK, there's no specific need to use NBS for brominating 'propiopiperone' :) , dioxane*Br2 should work as well.

3rd, this compound has been tested and reported as 'astounding'.




Antoncho

terbium

  • Guest
From safrole?
« Reply #6 on: September 29, 2002, 06:40:00 AM »
Where does the amine go if one adds methylamine to the epoxide formed via peracid oxidation of isosafrole?

PrimoPyro

  • Guest
Switched
« Reply #7 on: September 29, 2002, 01:50:00 PM »
Since The epoxide opens to give the more stable carbocation, and the amine attaches to the most stable carbocation, I would think the amine would be in the benzyl position, with the alcohol being at the isopropyl position.

PrimoPyro

Will perform sexual favors for females in exchange for 1,2-dimethylaziridine. PM for details.

Rhodium

  • Guest
Everything you need for methylone.
« Reply #8 on: September 29, 2002, 03:03:00 PM »
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation
Reagent   sodium methylate
Other Conditions   Erwaermen des Reaktionsprodukts mit Salzsaeure
Note 1    Handbook
Ref. 1    501525; Patent; Hesse; DE 88224; FTFVA6; Fortschr.Teerfarbenfabr.Verw.Industriezweige; DE; GE; 4; 1291.
Ref. 2    500436; Journal; Wallach; Pond; CHBEAM; Chem.Ber.; 28; 1895; 2719.
Ref. 3    500362; Journal; Hoering; CHBEAM; Chem.Ber.; 38; 1905; 3469; CHZEA6; Chem.Zentralbl.; GE; 77; II; 1906; 1223.

Reaction ID   741015
Reactant BRN   6224 benzo[1,3]dioxole-5-carbonitrile
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation
Reagent   ethyl magnesium bromide
   diethyl ether
Other Conditions   Erwaermen des erhaltenen 1-Benzo<1,3>dioxol-5-yl-propan-1-on-imins mit wss. Salzsaeure
Note 1    Handbook
Ref. 1    1997615; Journal; Fuson; Gaertner; Chadwick; JOCEAH; J.Org.Chem.; 13; 1948; 489, 493.


Reaction 15 of 34
Reaction ID   809025
Reactant BRN   82640 5-propenyl-benzo[1,3]dioxole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation
Reagent   phosphorus-pentachloride
Other Conditions   Zerlegung des Produkts mit Wasser und Kochen des mit Wasserdampf ueberdestillierten Oels mit alkoholischer Kalilauge
Note 1    Handbook
Ref. 1    500346; Journal; Schimmel & Co.; CHZEA6; Chem.Zentralbl.; GE; 76; I; 1905; 1470.
Ref. 2    501534; Book Review / Secondary Ref.; Schimmel & Co.; Bericht vom April 1905, 49.


Reaction 16 of 34
Reaction ID   1651712
Reactant BRN   115506 benzo[1,3]dioxole
   385632 propionyl chloride
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation
Yield   58 percent (BRN=165729)
Reagent   SnCl4
Solvent   CH2Cl2
Time   1 hour(s)
Temperature   20 C
Ref. 1    5702207; Journal; Daukshas, V. K.; Gaidyalis, P. G.; Pyatrauskas, O. Yu.; Udrenaite, E. B.; Gasperavichene, G. A.; Raguotene, N. V.; PCJOAU; Pharm.Chem.J.(Engl.Transl.); EN; 21; 5; 1987; 341-345; KHFZAN; Khim.Farm.Zh.; RU; 21; 5; 1987; 569-573.

Reaction 17 of 34
Reaction ID   1802483
Reactant BRN   150197 1-benzo[1,3]dioxol-5-yl-propan-1-ol
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation
Yield   64.06 percent (BRN=165729)
Reagent   chromium trioxide, concentrated H2SO4
Solvent   H2O
   acetone
Time   3 hour(s)
Temperature   0 - 20 C
Ref. 1    5677213; Journal; Alesso, Elba N.; Tombari, Dora G.; Iglesias, Graciela Y. Moltrasio; Aguirre, Jose M.; CJCHAG; Can.J.Chem.; EN; 65; 1987; 2568-2574.
Reaction 18 of 34
Reaction ID   1838008
Reactant BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
   1098229 methanol
Product BRN   155294 5-(1-methoxy-propyl)-benzo[1,3]dioxole
No. of Reaction Details   1
Reaction Classification   Preparation
Yield   81 percent (BRN=155294)
Reagent   NaBH4
Time   30 min
Temperature   20 C
Ref. 1    5519586; Journal; Daukshas, V. K.; Gaidyalis, P. G.; Udrenaite, E. B.; Labanauskas, L. K.; Gasperavichene, G. A.; et al.; PCJOAU; Pharm.Chem.J.(Engl.Transl.); EN; 23; 12; 1989; 990-995; KHFZAN; Khim.Farm.Zh.; RU; 23; 12; 1989; 1466-1470.
Reaction 19 of 34
Reaction ID   1838009
Reactant BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
   505995 formamide
Product BRN   5540275 N-1-(3,4-dimethoxyphenyl)propylformamide
No. of Reaction Details   1
Reaction Classification   Preparation
Yield   52.2 percent (BRN=5540275)
Time   8 hour(s)
Temperature   180 - 190 C
Ref. 1    5677213; Journal; Alesso, Elba N.; Tombari, Dora G.; Iglesias, Graciela Y. Moltrasio; Aguirre, Jose M.; CJCHAG; Can.J.Chem.; EN; 65; 1987; 2568-2574.
Reaction 20 of 34
Reaction ID   1838010
Reactant BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
Product BRN   150197 1-benzo[1,3]dioxol-5-yl-propan-1-ol
No. of Reaction Details   2
Reaction Classification   Preparation
Yield   90 percent (BRN=150197)
Reagent   LiAlH4
Solvent   diethyl ether
Time   30 min
Other Conditions   Heating
Ref. 1    5519586; Journal; Daukshas, V. K.; Gaidyalis, P. G.; Udrenaite, E. B.; Labanauskas, L. K.; Gasperavichene, G. A.; et al.; PCJOAU; Pharm.Chem.J.(Engl.Transl.); EN; 23; 12; 1989; 990-995; KHFZAN; Khim.Farm.Zh.; RU; 23; 12; 1989; 1466-1470.

Reaction ID   3824784
Reactant BRN   82642 5-trans-propenyl-benzo[1,3]dioxole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
   164033 benzo[1,3]dioxol-5-yl-propan-2-one
No. of Reaction Details   3
Reaction Classification   Chemical behaviour
Yield   18 percent (BRN=165729)
   60 percent (BRN=164033)
Reagent   O2
Catalyst   PdCl2/CuCl
Solvent   dimethylformamide
   H2O
Time   10 hour(s)
Temperature   50 C
Other Conditions   Reagents
Subject Studied   Product distribution
Ref. 1    5618292; Journal; Nagashima, Hideo; Sato, Koji; Tsuji, Jiro; TETRAB; Tetrahedron; EN; 41; 23; 1985; 5645-5652.
Reaction 23 of 34
Reaction ID   5261935
Reactant BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
Product BRN   8406937 1-benzo[1,3]dioxol-5-yl-2-chloro-propan-1-one
No. of Reaction Details   1
Yield   66 percent (BRN=8406937)
Reaction Classification   Preparation
Reagent   CuCl2*2H2O
   LiCl
Solvent   dimethylformamide
Time   6 hour(s)
Temperature   80 C
Reaction Type   Chlorination
Ref. 1    6206531; Journal; Zacchino, Susana A.; Lopez, Silvia N.; Pezzenati, German D.; Furlan, Ricardo L.; Santecchia, Carina B.; Munoz, Lorena; Giannini, Fernando A.; Rodriguez, Ana M.; Enriz, Ricardo D.; JNPRDF; J.Nat.Prod.; EN; 62; 10; 1999; 1353 - 1357.
Reaction 24 of 34
Reaction ID   5457190
Reactant   $a-<3.4-methylenedioxy-phenyl>-allylene
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation (half reaction)
Reagent   aqueous-alcoholic sulfuric acid
Note 1    Handbook
Ref. 1    500305; Journal; Foulds; Robinson; JCSOA9; J.Chem.Soc.; 105; 1914; 1966.



Reaction 26 of 34
Reaction ID   5457192
Reactant   1%1&-ethoxy-isosafrole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation (half reaction)
Reagent   hydrochloric acid
Note 1    Handbook
Ref. 1    500362; Journal; Hoering; CHBEAM; Chem.Ber.; 38; 1905; 3469; CHZEA6; Chem.Zentralbl.; GE; 77; II; 1906; 1223.
Reaction 27 of 34
Reaction ID   5457193
Reactant   1%1&-methoxy-isosafrole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation (half reaction)
Reagent   diluted hydrochloric acid
Note 1    Handbook
Ref. 1    500428; Journal; Tiffeneau; BSCFAS; Bull.Soc.Chim.Fr.; <4> 1; 1907; 1212.


Reactant   1%1&-methoxy-isosafrole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation (half reaction)
Reagent   diluted hydrochloric acid
Note 1    Handbook
Ref. 1    500428; Journal; Tiffeneau; BSCFAS; Bull.Soc.Chim.Fr.; <4> 1; 1907; 1212.
Reaction 28 of 34
Reaction ID   5457194
Reactant BRN   2037554 sulfuric acid
   135259 5-prop-1-ynyl-benzo[1,3]dioxole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Chemical behaviour
Note 1    Handbook
Ref. 1    504625; Book Review / Secondary Ref.; Robinson; Priv.-Mitt..
Reaction 29 of 34
Reaction ID   5457195
Reactant BRN   2036449 2-methyl-2-trideuteriomethoxy-propane
   82640 5-propenyl-benzo[1,3]dioxole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Chemical behaviour
Other Conditions   Zerlegung des Reaktionsprodukts mit Wasser und Kochen des mit Wasserdampf destillierten Oels mit alkoh. Kalilauge
Note 1    Handbook
Ref. 1    500429; Book Review / Secondary Ref.; Schimmel & Co.; Bericht vom April 1905, 49; C. 1905 I, 1470.
Reaction 30 of 34
Reaction ID   5457196
Reactant BRN   1098214 hydrochloric acid
   9790 1$x-ethoxy-1$x-benzo[1,3]dioxol-5-yl-propene
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Chemical behaviour
Note 1    Handbook
Ref. 1    500362; Journal; Hoering; CHBEAM; Chem.Ber.; 38; 1905; 3469; CHZEA6; Chem.Zentralbl.; GE; 77; II; 1906; 1223.
Reaction 31 of 34
Reaction ID   5457197
Reactant   chromic acid
Reactant BRN   150197 1-benzo[1,3]dioxol-5-yl-propan-1-ol
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Chemical behaviour
Note 1    Handbook
Ref. 1    500348; Journal; Mameli; AANLAW; Atti Accad.Naz.Lincei Cl.Sci.Fis.Mat.Nat.Rend.; <5> 13 II; 1904; 320; GCITA9; Gazz.Chim.Ital.; 34 II; 1904; 416.










--------------------------------

Melting Point 1-7 of 7
45 - 46   hexane      1
39      1   2-3
38      2   4
38.5      3   5
38   hexane   4   6
38 - 39      5   7
36 - 37         8
Note 1    Handbook
Note 2    Handbook
Note 3    Handbook
Note 4    Handbook
Note 5    Handbook
Ref. 1    5702207; Journal; Daukshas, V. K.; Gaidyalis, P. G.; Pyatrauskas, O. Yu.; Udrenaite, E. B.; Gasperavichene, G. A.; Raguotene, N. V.; PCJOAU; Pharm.Chem.J.(Engl.Transl.); EN; 21; 5; 1987; 341-345; KHFZAN; Khim.Farm.Zh.; RU; 21; 5; 1987; 569-573.
Ref. 2    501525; Patent; Hesse; DE 88224; FTFVA6; Fortschr.Teerfarbenfabr.Verw.Industriezweige; DE; GE; 4; 1291.
Ref. 3    500436; Journal; Wallach; Pond; CHBEAM; Chem.Ber.; 28; 1895; 2719.
Ref. 4    735496; Journal; Angeli; GCITA9; Gazz.Chim.Ital.; 22 II; 1892; 479; CHBEAM; Chem.Ber.; 25; 1892; 1960.
Ref. 5    504175; Journal; Ciamician; Silber; GCITA9; Gazz.Chim.Ital.; 23 II; 1893; 195, 202; GCITA9; Gazz.Chim.Ital.; 24 I; 1894; 431, 541.
Ref. 6    514935; Journal; Hillmer; Schorning; ZPCLAH; Z.Phys.Chem.(Leipzig); 168; 1934; 81, 104.
Ref. 7    1997615; Journal; Fuson; Gaertner; Chadwick; JOCEAH; J.Org.Chem.; 13; 1948; 489, 493.
Ref. 8    5677213; Journal; Alesso, Elba N.; Tombari, Dora G.; Iglesias, Graciela Y. Moltrasio; Aguirre, Jose M.; CJCHAG; Can.J.Chem.; EN; 65; 1987; 2568-2574.


-----------------------

Boiling Point 1-2 of 2
153 - 154   13   1   1-2
128   3.5   2   3
Note 1    Handbook
Note 2    Handbook
Ref. 1    501525; Patent; Hesse; DE 88224; FTFVA6; Fortschr.Teerfarbenfabr.Verw.Industriezweige; DE; GE; 4; 1291.
Ref. 2    500436; Journal; Wallach; Pond; CHBEAM; Chem.Ber.; 28; 1895; 2719.
Ref. 3    519826; Patent; Winthrop Chem. Co.; US 1964973; 1932.


--------------

CAS Registry Number   41103-34-8
Chemical Name   5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
   Isosafroldibromid
Autoname   5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Molecular Formula   C10H10Br2O2
Molecular Weight   322.00



Melting Point 1-4 of 4
51      1   1
52 - 53      2   2-3
52 - 53      3   2
51 - 52   pentane   4   4
Note 1    Handbook
Note 2    Handbook
Note 3    Handbook
Note 4    Handbook
Ref. 1    500366; Journal; Hoering; Baum; CHBEAM; Chem.Ber.; 42; 1909; 3080.
Ref. 2    500364; Journal; Waterman; Priester; RTCPA3; Recl.Trav.Chim.Pays-Bas; 48; 1929; 941.
Ref. 3    1534557; Journal; Mannich; ARPMAS; Arch.Pharm.(Weinheim Ger.); 248; 1910; 143; CHZEA6; Chem.Zentralbl.; GE; 80; I; 1909; 923.
Ref. 4    512137; Journal; Naves; Ardizio; BSCFAS; Bull.Soc.Chim.Fr.; 1957; 1053, 1056.

Reaction 5 of 20
Reaction ID   186589
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product BRN   135259 5-prop-1-ynyl-benzo[1,3]dioxole
No. of Reaction Details   1
Reaction Classification   Preparation
Reagent   diethylene glycol
   potassium hydroxide
Note 1    Handbook
Ref. 1    512718; Journal; Nelb; Tarbell; JACSAT; J.Amer.Chem.Soc.; 71; 1949; 2936.
Reaction 6 of 20
Reaction ID   186590
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product BRN   150217 5-(2-bromo-propenyl)-benzo[1,3]dioxole
No. of Reaction Details   1
Reaction Classification   Preparation
Other Conditions   Bei der Destillation unter vermindertem Druck
Note 1    Handbook
Ref. 1    500305; Journal; Foulds; Robinson; JCSOA9; J.Chem.Soc.; 105; 1914; 1966.
Reaction 7 of 20
Reaction ID   186591
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product BRN   165729 1-benzo[1,3]dioxol-5-yl-propan-1-one
No. of Reaction Details   1
Reaction Classification   Preparation
Reagent   sodium methylate
Other Conditions   Erwaermen des Reaktionsprodukts mit Salzsaeure

Note 1    Handbook
Ref. 1    501525; Patent; Hesse; DE 88224; FTFVA6; Fortschr.Teerfarbenfabr.Verw.Industriezweige; DE; GE; 4; 1291.
Ref. 2    500436; Journal; Wallach; Pond; CHBEAM; Chem.Ber.; 28; 1895; 2719.
Ref. 3    500362; Journal; Hoering; CHBEAM; Chem.Ber.; 38; 1905; 3469; CHZEA6; Chem.Zentralbl.; GE; 77; II; 1906; 1223.
Reaction 8 of 20
Reaction ID   186592
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product BRN   171391 1-benzo[1,3]dioxol-5-yl-2-bromo-propan-1-ol
No. of Reaction Details   2
Reaction Classification   Preparation
Reagent   aqueous acetone
   marble
Note 1    Handbook
Ref. 1    500356; Patent; Hoering; DE 174496.
Ref. 2    500362; Journal; Hoering; CHBEAM; Chem.Ber.; 38; 1905; 3469; CHZEA6; Chem.Zentralbl.; GE; 77; II; 1906; 1223.
Reaction 9 of 20
Reaction ID   809028
Reactant BRN   82640 5-propenyl-benzo[1,3]dioxole
Product BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
No. of Reaction Details   3
Reaction Classification   Preparation
Reagent   diethyl ether
   bromine
Note 1    Handbook
Ref. 1    500360; Journal; Wallach; Pond; CHBEAM; Chem.Ber.; 38; 1905; 2719.

Reaction 14 of 20
Reaction ID   5400404
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product   1%2&-bromo-isosafrole
No. of Reaction Details   1
Reaction Classification   Chemical behaviour (half reaction)
Other Conditions   Bei der Destillation unter vermindertem Druck
Note 1    Handbook
Ref. 1    500305; Journal; Foulds; Robinson; JCSOA9; J.Chem.Soc.; 105; 1914; 1966.
Reaction 15 of 20
Reaction ID   5461129
Reactant BRN   3587193 Br2
   1696894 diethyl ether
   82640 5-propenyl-benzo[1,3]dioxole
Product BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
No. of Reaction Details   1
Reaction Classification   Chemical behaviour
Note 1    Handbook
Ref. 1    500436; Journal; Wallach; Pond; CHBEAM; Chem.Ber.; 28; 1895; 2719.
Reaction 16 of 20
Reaction ID   5461130
Reactant   cis-isosafrole
Product BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
No. of Reaction Details   1
Reaction Classification   Preparation (half reaction)
Reagent   diethyl ether
   bromine
Note 1    Handbook
Ref. 1    512137; Journal; Naves; Ardizio; BSCFAS; Bull.Soc.Chim.Fr.; 1957; 1053, 1056.
Reaction 17 of 20
Reaction ID   5461132
Reactant   trans-isosafrole
Product BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
No. of Reaction Details   1
Reaction Classification   Preparation (half reaction)
Reagent   diethyl ether
   bromine
Temperature   -10 C
Note 1    Handbook
Ref. 1    512137; Journal; Naves; Ardizio; BSCFAS; Bull.Soc.Chim.Fr.; 1957; 1053, 1056.
Reaction 18 of 20
Reaction ID   5574136
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Reactant   isosafrole bromohydrin
Product BRN   357396 bis-(1-benzo[1,3]dioxol-5-yl-2-bromo-propyl)-ether
No. of Reaction Details   1
Reaction Classification   Preparation
Other Conditions   im verschlossenen Gefaess
Note 1    Handbook
Ref. 1    969731; Journal; Mannich; Schmitt; ARPMAS; Arch.Pharm.(Weinheim Ger.); 1928; 80; CHZEA6; Chem.Zentralbl.; GE; 98; I; 1927; 951.
Reaction 19 of 20
Reaction ID   5574947
Reactant BRN   171390 5-(1,2-dibromo-propyl)-benzo[1,3]dioxole
Product   1%2&-bromo-isosafrole
Product BRN   3587158 hydrogen bromide
No. of Reaction Details   1
Reaction Classification   Chemical behaviour
Note 1    Handbook
Ref. 1    500364; Journal; Waterman; Priester; RTCPA3; Recl.Trav.Chim.Pays-Bas; 48; 1929; 941.


starlight

  • Guest
microwave acylation
« Reply #9 on: October 01, 2002, 11:30:00 AM »
Rapid microwave-promoted synthesis of functionalised benzophenones
David A. Learmonth
Synthetic Communications, Volume 32, Issue 18, Pages 2757-2762

Abstract
Several functionalised benzophenone derivatives have been conveniently obtained in moderate to good yield via the rapid, microwave-promoted Friedel–Crafts acylation of activated arenes with benzoic acids in polyphosphoric acid medium.

...

Reactions were run in open borosilicate round-bottom glass vessels at atmospheric pressure in a microwave oven adapted for organic synthesis (focussed microwaves on reaction vessel; continuous un-pulsated power regulation; microwave cavity dimensions: height 210 mm, width 290 mm, depth 320 mm; incorporated magnetic stirrer, infra-red temperature sensor and overfield sensor).

A typical experimental procedure for the microwave-promoted synthesis of benzophenones is exemplified by the following example:

3,4-Dimethoxy-4-methyl-benzophenone (Run 1): Polyphosphoric acid (15 g) was added to veratrole (1.0 g, 7.25 mmo1) and p-toluic acid (1.08 g, 7.97 mmo1) in an open 50 mL round bottom flask equipped with a magnetic stirring bar. The mixture was placed in the cavity of the microwave oven and irradiated at 100% power for 45 s, with the maximum allowed temperature set at 120 deg C. The resulting deep red mixture was allowed to cool, and then poured onto ice/water (100 mL). The precipitate was filtered off, washed with water and dried in air. Recrystallisation (iPrOH) afforded the product as beige crystals, 1.52 g, (82%) of m.p. 127-128 deg C.

Rhodium

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Forensic Methylone Investigation
« Reply #10 on: October 01, 2002, 02:34:00 PM »
Seems like I forgot to post this forensic article about methylone analogs:

The characterization of some 3,4-methylenedioxycathinone (MDCATH) homologs
Terry A. Dal Cason

Forensic Science International Volume 87, Issue 1, 9-53 (1997)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/methylenedioxycathinone.pdf)
DOI:

10.1016/S0379-0738(97)02133-6



Abstract
In the past 35 years, a wide variety of illicit drugs have appeared in the clandestine market. Many of these compounds are based on the structure of amphetamine (1-phenyl-2-aminopropane) to which various functional or structural groups have been added. Previous modifications to the amphetamine molecule include addition of a methylenedioxy bridge to give 3,4-methylenedioxyamphetamine, and attachment of alpha,beta-keto oxygen to yield cathinone. A chemical synthesis integrating the salient functional/structural groups of these two classes of amphetamine analogs results in manufacture of methylenedioxycathinone (MDCATH). In each instance, N-alkylation of these analogs provides a series of homologs. Furthermore, many of these analogs/homologs meet several criteria which typically support the clandestine laboratory synthesis of novel illicit drugs (`designer drugs'). The MDCATH analogs represent a potentially new series of `designer drugs' whose chemical characteristics have not previously been reported. Appropriate selection of analytical, chemical and physical tests will enable rapid identification of these analogs by a comparative analysis using the data provided.

Rhodium

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Cathinone: Investigation of several analogs
« Reply #11 on: December 09, 2003, 09:17:00 PM »
Cathinone: An investigation of several N-alkyl and methylenedioxy-substituted analogs
DalCason TA, Young R, Glennon RA

Pharmacology Biochemistry and Behavior 58(4), 1109-1116 (1997)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/cathinone-methylone.pdf)
DOI:

10.1016/S0091-3057(97)00323-7



Abstract
Structurally, methcathinone is to cathinone what methamphetamine is to amphetamine. Due to increased interest in the abuse of suck agents we wished to determine if certain derivatives of cathinone would behave in a manner consistent with what is known about their amphetamine counterparts; that is, can amphetamine structure-activity relationships be extrapolated to cathinone analogs? As expected on the basis of known structure-activity relationships for amphetaminergic agents, both N-monoethylcathinone and N-mono-n-propylcathinone (N-Et CAT and N-Pr CAT; ED50 = 0.77 and 2.03 mg/kg, respectively) produced amphetamine-like stimulus effects in rats trained to discriminate 1 mg/kg of (+)amphetamine from Vehicle and were somewhat less potent than racemic methcathinone. In contrast, (-)N,N-dimethylcathinone or (-)Di Me CAT (ED50 = 0.44 mg/kg) was more potent than expected; although (+)N,N-dimethylamphetamine is sevenfold less potent than (+)methamphetamine, (-)Di Me CAT is only about 1.6-fold less potent than (-)methcathinone, and is essentially equipotent with (-)cathinone. In addition, although it has been previously demonstrated that 1-(3,4-methylenedioxyphenyl) -2-aminopropane (MD A) results in stimulus generalization in rats trained to discriminate (+)amphetamine or DOM from vehicle; the cathinone counterpart of MDA (i.e., MDC) resulted in partial (maximum: 58%) generalization in (+)amphetamine-trained animals, and failed to produce >7% DOM-appropriate responding in rats trained to discriminate DOM from vehicle. On the other hand, the N-methyl analog of MDC (i.e., MDMC) behaved in a manner similar to that of the N-methyl analog of MDA (i.e., MDMA); that is, st (+)amphetamine stimulus (MDMC: ED50 = 2.36 mg/kg) but not a DOM stimulus generalized to MDMC. In MDMA-trained rats, stimulus generalization occurred both to MDC and MDMC (ED50 = 1.64 and 1.60 mg/kg, respectively). Although this and previous studies have demonstrated that significant parallelisms exist between the structure-activity relationships of amphetamine analogs and cathinone analogs, we now report several unexpected qualitative and/or quantitative differences. It is suggested that caution be used in attempting to draw conclusions or make predictions about the activity and potency of novel cathinone analogs by analogy to the structure-activity relationships derived from amphetamine-related agents; it would appear that each new cathinone analog will require individual investigation.

Abstract posted earlier in

Post 108548 (missing)

(dormouse: "Methylenedioxy-cathinone analogs  -Lone Deranger", Novel Discourse)

Rhodium

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A two-step method for chiral cathinones
« Reply #12 on: December 09, 2003, 09:48:00 PM »
A two-step method for the preparation of homochiral cathinones
M. Osorio-Olivaresa, M. C. Rezende, S. Sepúlveda-Bozab, B. K. Cassels, R. F. Baggio, J. C. Muñoz-Acevedoe

Tetrahedron: Asymmetry 14(11), 1473-1477 (2003)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/two-step.chiral.cathinone.pdf)
DOI:

10.1016/S0957-4166(03)00317-3



Abstract
A simple method for the preparation of homochiral ring-substituted 1-aryl-2-aminopropanones 2 (`cathinones´) is described, involving initial Friedel–Crafts acylation of aromatics with (S)- or (R)-N-trifluoroacetylalanyl chloride, followed by acid hydrolysis of the intermediate trifluoroacetamido intermediates 1, for which X-ray diffraction analysis confirmed the structures.



(S)-N-Trifluoroacetylalanine

1,1,3,3-Tetramethylguanidine (3.75 mL, 30 mmol) was added to a suspension of L-alanine (2.0 g, 22 mmol) in MeOH (11 mL). After 5 min, ethyl trifluoroacetate (3.3 mL, 28 mmol) was added and the reaction was stirred for 4 h at room temperature. The solvent was then removed by rotary evaporation and the residue dissolved in H2O (35 ml) and acidified with concentrated HCl (4 mL). After stirring for 15 min, the mixture was extracted with EtOAc (2×30 mL) and the organic layers were combined and washed with brine (30 mL), dried over Na2SO4 and rotary evaporated to give a solid which was washed with n-hexane and dried to afford the crude amide, mp 62–64°C, yield 3.5 g (86%), sufficiently pure for all subsequent uses.

General procedure for the preparation of (S)-2-trifluoroacetamido-1-aryl-1-propanones 1

To a stirred suspension of (S)-N-trifluoroacetylalanine (1 g, 5.4 mmol) in dry CH2Cl2 (20 mL), cooled to 0°C in an ice-water bath, was added oxalyl chloride (1.1 mL, 12.8 mmol) followed by pyridine (1 drop). The reaction mixture was allowed to warm gradually to room temperature and was then stirred further for 5 h. The solvent and excess oxalyl chloride were removed by rotary evaporation at 35°C to afford the crude acid chloride. To this chloride was then added with stirring a solution of the aromatic compound (5.4 mmol) in CH2Cl2 (5 mL), followed by AlCl3 (0.72 g, 5.4 mmol) and the resulting mixture was allowed to react for 18 h. The reaction mixture was then cooled in an ice-water bath and slowly quenched with 1N HCl (30 mL) and CH2Cl2 (30 mL). The aqueous layer was extracted with CH2Cl2 (2×30 mL) and the organic layers were combined, dried over Na2SO4, and rotary evaporated to give the crude product 1, which was crystallized in hexane.

General procedure for the preparation of (S)-2-amino-1-aryl-1-propanone hydrochlorides 2

The (S)-2-trifluoroacetamido-1-aryl-1-propanone derivatives 1 (0.7 mmol) were dissolved in 2-propanol (16 mL) and concentrated HCl (12 mL). The resulting solutions were then stirred at 40°C for 12 h. Elimination of the solvent by rotary evaporation, followed by addition of diethyl ether (15 mL) and 2-propanol (0.5 mL) precipitated the hydrochloride salts 2.

Rhodium

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Friedel-Crafts Acylation with N-Acylamino Acids
« Reply #13 on: October 22, 2004, 10:02:00 PM »
?-Amino Acids as Chiral Educts for Asymmetric Products. Amino Acylation with N-Acylamino Acids
Thomas F. Buckley III and Henry Rapoport

J. Am. Chem. Soc., 103, 6157-6163 (1981)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/fc-acylation.n-carbamyl-alpha-amino-acyl-chlorides.pdf)

Abstract
?-N-Acylamino acids have been developed as useful reagents for the preparation of optically pure ?-aminoalkyl aryl ketones. Protection of the amino group as either the ethoxycarbonyl or benzenesulfonyl derivative allows alanine to serve as an effective educt for the chirally specific synthesis of a variety of structures containing the phenylethylamine backbone. Benzene undergoes Friedel-Crafts acylation with the N-acylalanine acid chloride? Catalyst complexation with oxygenated aromatics, however, prohibits acylation of aryl ethers. An arylmetallo reaction scheme overcomes this problem and also affords regiospecificity not attainable in conventional acylations. As examples, optically pure ephedrines and amphetamines were directly synthesized without recourse to resolution since the chirality of the amino acid educt was entirely conserved throughout the process.


somuchclass

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MDECAT
« Reply #14 on: October 28, 2004, 07:33:00 PM »
I have tried methylone (MDMCAT) for myself; in fact, I did a total of 6 grams of it, and I have heard of someone at the hive mentioning having intoxicating himself on MDCAT, but does anyone here have any information or personal experience with the N-ethyl homologue of methylone, MDECAT?

phenethyl_man

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methylone from gringards
« Reply #15 on: October 29, 2004, 09:28:00 AM »
rhodium;  so I take it from the article that the following could be a viable route?


DL-alanine + benzenesulfonyl chloride -> N-benzenesulfonylalanine

N-benzenesulfonylalanine -> N-benzenesulfonylalanyl chloride

benzodioxole -> 3,4-methylenedioxyphenylmagnesium bromide

3,4-methylenedioxyphenylmagnesium bromide (2 molar eq.) + N-benzenesulfonylalanyl chloride -> 2-((Benzenesulfonyl)amino)-1-(3,4-methylenedioxyphenyl)-1-propanone

2-((Benzenesulfonyl)amino)-1-(3,4-methylenedioxyphenyl)-1-propanone -> 2-((Benzenesulfonyl)-methylamino)-1-(3,4-methylenedioxyphenyl)-1-propanone

2-((Benzenesulfonyl)-methylamino)-1-(3,4-methylenedioxyphenyl)-1-propanone -> 2-(methylamino)-1-(3,4-methylenedioxyphenyl)-1-propanone (Methylone)