Alkylamination of Aromatic Derivatives

java · Consumer

Cyclic Carbamates as Reagents for Alkylamination of Aromatic Derivatives under Friedel-Crafts Conditions
C. Jouitteau, P.LePerchec, A.Forestiere, B. Sillion
Tetrahedron Letters vol.21,1719-1722, 1980

DJVU

Abstract
Aryl(ethyl-) and propylamines are obtained with good yields by a decarboxylation-alkylation process applied on aluminum trichloride-cyclic carbamate complexes. The coupling of two aromatic units is observed in the case of oxazolidinone-toluene reaction.

IndoleAmine · Dreamreader Deluxe

Wait... let me guess: virtually all subst. phenylisopropylamines directly, one-step from the corresponding substituted benzenes and carbamates via FC - right?

Cool

java · Consumer

Correct, like everything I post, they are tools for needed steps in the respective chemistry. some can see the use , while for others it will take a while to find the use .....I just gather and hope it's of some use to someone........java

pharmakon · Fri Mar 04, 2005 3:35 am

PEA seems easy accessible ... Idea

double Mannich

NPP
In that Teterahedron-article two references about the synthesis of cyclic carbamates are mentioned:

(6) M.E. Dyen and D. Swern, Chem. Rev., 197 t 2, 1967

(7) B.L. Phillips and P.A. Argabricht, J. Heterocyclic Chem., 3, 84, 1966

Please, can anybody scan and post these articles ?

Thanks alot ! Very Happy

Guest · Fri Mar 04, 2005 9:28 am

There are two papers dealing with the double mannich form PEA,
They are clear and easy to follow,
They were in the serious chemistry, which is a more complete version is being upload this week,

I will hopefully be able to get those articles you talk of,
but not for a couple of weeks,

Yes,
They are valubale and need ocr'ing,

syn

pharmakon · Sun Mar 06, 2005 11:30 pm

2-Oxazolidinone and its 4,5-Alkyl substituents are most important for this method. Here is a preparation method for the basic 2-Oxazolidone

1. Procedure
A 2-L, three-necked flask equipped with a thermometer, magnetic stirring bar, and a Vigreux column fitted with a distillation head is charged with 305 g (5.0 mol) of freshly distilled 2-aminoethanol, 730 g (6.2 mol) of diethyl carbonate, and 2.5 g (0.05 mol) of sodium methoxide (Note 1). The mixture is stirred and the flask is heated in an oil bath maintained at 125–130°C. Ethanol begins to distill off when the internal temperature reaches 95–100°C. After heating for about 8 hr, the internal temperature reaches 125°C and ethanol ceases to distill (Note 2). The reaction mixture is allowed to cool to 60–70°C and is poured into 1 L of cold chloroform (Note 3). The resulting solution is chilled thoroughly in an ice–water bath and the precipitated product is recovered by filtration. The filtrate is concentrated to 250 mL and chilled to give a second crop. The combined crops are dried in a vacuum oven at 50°C to give 320–339 g (74–78%) of white crystals, mp 86–88°C [lit.2 mp 87–89°C] (Note 4).

2. Notes
1. The checkers obtained 2-aminoethanol, diethyl carbonate, and anhydrous sodium methoxide from the Aldrich Chemical Company.
2. About 625 mL (theoretical: 583 mL) of ethanol is collected. If the reaction is stopped before this volume is collected, the yield is reduced.
3. If the reaction mixture cools below 60°C, the product solidifies in the flask.
4. The product shows the following 1H NMR spectrum (d6-DMSO) δ: 3.3–3.8 (m, 2 H), 4.2–4.6 (m, 2 H), 6.5–7.5 (br s, 1 H) and is analytically pure. Anal. calcd. for C3H5NO2: C, 41.38; H, 5.79; N, 16.09. Found: C, 41.61; H, 5.70; N, 16.06. The submitters report that they obtained pure material, mp 89–90°C, after three recrystallizations from chloroform.

see for more details: Homeyer, A. H. U.S. Patent 2399118, 1946, Chem. Abstr. 1946, 40, 4084.

Still that article from E.Dyen and Daniel Swern would be most interesting ... Smile

[/b]

Lief · Tue Mar 08, 2005 5:01 pm

Check out these patents:

US 2701246 Method of preparing a cyclic carbamate

US 2744897

US 2891058 Process for the preparation of n-vinyl cyclic amides, carbamates, and lactams
N-vinyl-2-oxazolidinones, etc.

US 2993031 Nu-isopropenyl-cyclic carbamate compounds and polymers thereof

US 2977369 Production of 2-oxazolidinones

US 2842523 Beta-amino lower-alkyl carbamates and resinous reaction products thereof

US 2860043 Method of regulating plant growth
EXAMPLE I Part A
Preparation of 2-oxazolidinone. -- Into a 300 ml., 3 neck flask equipped with a
thermometer, stirrer, and air reflux condenser are introduced 61 gms. of
ethanolamine and 60 gms. of urea. Heating and stirring are continued for
2 1/2 hours, the temperature being maintained within the range from about
135°-150° C. The crude reaction product is a clear pale yellow liquid, which is
vacuum distilled to remove unreacted ethanolamine. The distilled product is
dissolved in 50 ml. of hot chloroform and filtered. The filtrate is cooled to
precipitate a white crystalline material, which is then washed with a small
amount of cold chloroform and dried. This product is recrystallized from
chloroform to obtain a product having a melting point range from 85°-90° C.
and has the following analysis:

US 2865926 Process of making 3-substituted-2-oxazolidinones

US 2975187 Cyanoethylated oxalactams
EXAMPLE II Preparation of 2-oxazolidinone
To a stainless steel autoclave were charged 244 grams Of ethanolamine (4 moles) and 352
grams of carbon dioxide (8 moles). The autoclave was sealed and heated at a temperature of
135° C. and at a pressure of 1000 p.s.i.g. for a period of seven hours. Following this, the
autoclave was drained and 220 grams of monoethanolamine were removed by distillation. The
remaining residue was allowed to cool and solidify, and was then crystallized from acetone.
About 36 grams of 2-oxazolidinone were recovered in this manner. This represented a yield
of about 10.3 percent of theoretical. This material had a melting point
of 90-90.5° C. Analysis.-Calculated for C3H5NO2: N, - 16.1 %. Found: N,
16.08%.

US 3133932 Production of 2-oxazolidinones
Example 3
Urea, 12.0 parts, and ethanolamine, 12.2 parts, in 100 parts
dimethylformamide as a solvent were heated under reflux at about 160° C. in the
apparatus described in Example 1 for 5 hours. During the reaction period
100% of the theoretical amount of ammonia was evolved. The solvent was removed
from the reaction nixture by distillation under reduced pressure, and the
residue recrystallized from methyl ethyl ketone to give 14.1 parts 2-oxazolidinone,
representing 81% of the theoretical yield.
Example 4
Urea, 12.0 parts, and ethanolamine, 12.2 parts, in 100 parts tetramethylurea as a
solvent were heated under reflux 65 at about 160° C. in the apparatus described
in Example 1 for 4 hours. During the reaction period, 100% of the theoretical
amount of ammonia was evolved. The solvent was removed from the reaction
mixture by distillation under reduced pressure, and the residue recrystallized from methyl
ethyl ketone to give 15.1 parts (86.8% of theory) of 2-oxazolidinone.

US 4521626
method for preparing 5-methyl-2-oxazolidinones in high yields and selectivities
by the reaction of urea with propylene carbonate.

US 6271388 Process for producing oxazolidin-2-one derivative
from 1,3-dioxolan-2-one derivative and urea

US 4405794 Preparation of 2-oxazolidinone and ethyleneurea

US 2627524 Hydroxy carbamates and process of producing same

serine -?-> ethanolamine + CO2

java · Consumer

Sometimes it helps to put down as much information about a wanted reference in order for the researcher to locate it.......java
Note:
this references are needed.....and maybe should be in the wanted reference thread.....which they will also be listed
--------------------------------------------------------------------------------------

Reaction of Inorganic Cyanates with Halides. II. Reactions of Chlorohydrins
Brian L. Phillips, Perry A. Argabright
J. Hetrocyclic Chemistry 1966, Volume 3, pp. 84-89

Abstract
The reaction of ethylene and trimethylene chlorohydrins with cyanate ion in anhydrous dimethylformamide (DMF) forms 2-oxazolidinone and tetrahydro-2H-1,3-oxazin-2-one, respectively. These are the major products over a wide concentration range, and at initial chlorohydrin concentration of 1 M and lower, the yields are high enough to make the reaction useful for synthesis of oxazine and oxazolidine derivatives. The corresponding reaction with tetramethylene chlorohydrin gave tetrahydrofuran as the major product with the by - products being polymeric. Pentamethylene and hexamethylene chlorohydrins yield linear polyurethanes when allowed to react with cyanate in DMF. Examination of the relative rates of reaction of these chlorohydrins indicate that the mechanism by which urethanes are formed (both cyclic and polymeric) is an SN2 displacement of chloride by cyanate ion to give an isocyanate intermediate which then reacts with an alcohol group to form urethane.

------------------------------------------------------------------------------------
2-Oxazolidones
Martin E. Dyen and Daniel Swern
Chem. Rev. 197 - 246, 1967

the first page with contents is here

Lief · Sat Mar 19, 2005 8:06 pm

Here's the Journal of Heterocyclic Chemistry article: http://home.ripway.com/2004-2/71090/Chemarticles/jhc1966-84-89.djvu

Lief · Thu Mar 24, 2005 7:12 am

I copied pages 197 to 236 of the Chemical Reviews article (without most of the references at the end):
http://rapidshare.de/files/981649/chemrev1967-197-236.djvu.html
I'll copy and upload the rest of the references later.

Lief · Sat Mar 26, 2005 9:24 pm

Here's the rest of the references: http://rapidshare.de/files/1012540/chemrev1967-237-246.djvu.html

pharmakon · Fri Apr 15, 2005 8:22 pm

Now, that we learned about the synth of oxazolidones, it would be great to know, how to synthesize 2-Aminoalcohols, for example 2-(N-methyl)propan-1-ol-amin. Any suggestions ? I'm eager to learn Exclamation

IndoleAmine · Dreamreader Deluxe

Reductive amination of 3-hydroxypropanal with methylamine over Zn/molecular sieves, or maybe with NaBH4 - works 100% sure (Al/Hg could be capable of doing the trick as well, and several other dissolving metal reductions probably too...)

The required 3-OH-propanal aldehyde can be made by partial oxidation of 1,3-propanediol with 0.5x needed molar amount of Jones Reagent for example, maybe sodium persulfate works too.

And also most probably useful for making said hydroxyaldehyde from propanediol is the following selective oxidation with NaNO2/acetic anhydride posted by Java:
http://rapidshare.de/files/1134475/OxidationNaNO2.djvu.html

i_a

anime · Sat Apr 16, 2005 5:52 am

Anyway to hydrolyze sulfonic acids to alcohols? because taurine (amino acid) is a 2-aminoethanesulfonic acid.

IndoleAmine · Dreamreader Deluxe

Hehe, sounds familiar - l-alanine is l-alpha-aminopropanoic acid, nyarlothotep is currently working on a nitroethane synth by decarboxylation of alanine to 2-aminoethane followed by oxidation...
(maybe one could make nitroethane via 2-nitroethanol made from taurine this way? Laughing

)

i_a