Dimethyltryptamine

[Rhodium]

Psychokitty: Could you remind me of applicable references to this Ti(iPrO)4 reductive amination? 

http://rhodium.lycaeum.org

[slothrop]

Journal of Organic Chemistry 60: 4928-4929, 1995 -  Reductive Alkylations of Dimethylamine Using Titanium(IV) Isopropoxide and Sodium Borohydride: An Efficient, Safe, and Conventient Method for the Synthesis of N,N-Dimethylated Tertiary Amines

Tetrahedron Letters 35,xx: 2401-2404, 1994 - Titanium(IV) Isopropoxide and Sodium Borohydride: A Reagent of Choice for Reductive Amination

These two might be of interest.

//Tyrone Slothrop

[smiley_boy]

Slothrop,

Hey, another Thomas Pynchon fan! Wow, this place is chock-a-blok with nerds, isn't it?  

I wanted to add to your list the following suggestions:

Titanium(IV) isopropoxide mediated solution phase reductive amination on an automated platform: application in the generation of urea and amide libraries.    
Comb Chem High Throughput Screen 3(2), 117-24 (2000)

Post 445976

(Rhodium: "Titanium(IV)Isopropoxide Reductive Amination", Tryptamine Chemistry)

A single-step reductive amination of carbonyl compounds with polymethylhydrosiloxane-Ti(OiPr)4.   
Synlett (11), 1655-1657 (2000)

Post 170334

(Lilienthal: "Novel reductive amination with PMHS-Ti(OiPr)4", Novel Discourse)

1-(N,N-Dimethylamino)adamantane.   
Molecules  (2000),  5(4),  M159.

A high throughput synthesis of N,N-dimethyl tertiary amines.
Synth. Commun. (2000),  30(11),  2001-2008.

Facile preparation of N-methyl secondary amines by Ti(iPrO)₄-mediated reductive amination of carbonyl compounds.    J. Chem. Soc., Perkin Trans. 1  (1998),   (16),  2527-2532.

Titanium(IV)mediated reductive aminations of 1-adamantyl methyl ketone: facile preparation of potential antiviral agents rimantadine and its analogs.     J. Chem. Soc., Perkin Trans. 1  (1995),   (14),  1845-7.

And of course:

J. Org. Chem. 55, 2552 (1990)

[Mr_D]

In

Post 270917

(Lilienthal: "Re: DMT synthesis 3", Tryptamine Chemistry), Lilienthal says that the freebase doesn't crystallize from raw ethyl acetate solution. So is it a salt when it's extracted from the reaction mixture? This proceedure has been done by others and the product has been determined to be good DMT, correct? Thanks.

[Rhodium]

Recrystallize from hexane (petroleum ether) instead. Reference:

http://www.drugsinfo.net/tihkal/tihkal06.html

[Rhodium]

There seems to be hope - Imagine the aldehyde being formaldehyde instead...

Unfortunately, what can be seen in that image is all that can be read in that article - the image, the text, and the associated references is something I just cut and pasted together to form an "abstract" - the article is a very brief communication, so it leaves a lot to the imagination...

Edit: I just realized that the "NaBH₄" part might be a typo, as the article they reference is this one:

JACS 93, 2897-2904 (1971)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/cyanoborohydride.review.borch.pdf)

[Rhodium]

As mentioned in

Post 184126

(smiley_boy: "Re: Dimethyltryptamine", Tryptamine Chemistry):

Titanium(IV)Isopropoxide Mediated Solution Phase Reductive Amination on an Automated Platform
S. Bhattacharyya ; L. Fan ; L. Vo ; J. Labadie

Combinatorial Chemistry & High Throughput Screening, Vol 3, No 2, pp 117-124 (2000)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/redamin.ti-isopropoxide.combchem.pdf)

Abstract

Amine libraries and their derivatives are important targets for high throughput synthesis because of their versatility as medicinal agents and agrochemicals. As a part of our efforts towards automated chemical library synthesis, a titanium(IV) isopropoxide mediated solution phase reductive amination protocol was successfully translated to automation on the Trident ä library synthesizer of Argonaut Technologies. An array of 24 secondary amines was prepared in high yield and purity from 4 primary amines and 6 carbonyl compounds. These secondary amines were further utilized in a split synthesis to generate libraries of ureas, amides and sulfonamides in solution phase on the Trident. The automated runs included 192 reactions to synthesize 96 ureas in duplicate and 96 reactions to synthesize 48 amides and 48 sulfonamides. A number of polymer-assisted solution phase protocols were employed for parallel work-up and purification of the products in each step.

[freakyDMT]

my experience is that adding sodiummethoxide at the KrZ DMT syntheses highers the yield considerable,
i make the pH above 9 which is more logic and a reactiontime of 60 hrs. is overdone!
see post 28474 JMC 44(23)3881/2001,and i use the Hcl salt
yield 75-80% minimum!
about the considerable differences in meltingpoints of DMT,my experience is that DMT freebase can hold solvents for a very long time,because its so waxy,that explains,i guess,the differences.

[Rhodium]

As mentioned in

Post 181778

(sunlight: "Re: Dimethyltryptamine", Tryptamine Chemistry)

Borohydride Reductions in Dichloromethane:
A Convenient, Environmentally Compatible Procedure for the N-Methylation of Amines
Sukanta Bhattacharyya

Synthetic Communications, 25(14), 2061-2069 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/n-methylation.zn-borohydride.pdf)

Abstract
The combination of zinc chloride and sodium borohydride in dichloromethane is used to effect reductive aminations of formaldehyde with a variety of primary and secondary amines containing potentially acid-sensitive functional groups in good to excellent yields.