Author Topic: New P2P syntheses from industrial chemicals  (Read 3679 times)

0 Members and 1 Guest are viewing this topic.

Rhodium

  • Guest
New P2P syntheses from industrial chemicals
« on: February 26, 2003, 04:19:00 AM »
According to

Chem. Ber. 60, 1050-69 (1927)

(https://www.thevespiary.org/rhodium/Rhodium/djvu/hydratropaldehyde.djvu) P2P can be made not only from H2SO4 treatment of 2-phenylpropanal (hydratropaldehyde), but also from 2-phenyl-1,2-propandiol and its corresponding epoxide, alpha-methylstyrene epoxide.

I need help to translate the pertinent parts of the above article though (the mechanism discussion + experimental).

DjVu browser plugin

(http://www.djvu.com/download/)

Osmium

  • Guest
I remember seeing a patent where hydratropic...
« Reply #1 on: February 26, 2003, 05:01:00 PM »
I remember seeing a patent where hydratropic aldehyde was rearranged in the vapor phase, by using solid catalysts. Maybe someone remembers the patent numbers? I know I wrote it down somewhere, but can't find it anymore.


Rhodium

  • Guest
hydratropaldehyde
« Reply #2 on: February 26, 2003, 10:21:00 PM »
Osmium: You are probably looking for

Patent US4694107

. Can you please help with the translation of the above?

Rhodium

  • Guest
HOI: Safrole to MDP2P & a-Me-Styrene to P2P
« Reply #3 on: March 02, 2003, 06:33:00 AM »
Once upon a time, close to a hundred years ago, it seems like the frenchmen invented a simple way of turning Safrole to MDP2P as well as alpha-methylstyrene to P2P using something as simple as hypoiodous acid (HOI) and simple heating with acids & bases. However, to obscure their discovery as much as possible for the rest of the world, they encrypted their findings by publishing it in french (PGP was not available at the time). Luckily we have cryptography experts here at the Hive (Hypo & Chimimanie) who are specializing in this ancient cryptographic language, so we may soon find out what the frenchmen's secret was...



Bull. Soc. Chem. France 310-321 (1908)

(https://www.thevespiary.org/rhodium/Rhodium/djvu/tiffeneau52-53.djvu)

Bull. Soc. Chem. France 322-331 (1908)

(https://www.thevespiary.org/rhodium/Rhodium/djvu/daufresne54-55.djvu)

Rhodium

  • Guest
Glycols, halohydrins & epoxides to P2P
« Reply #4 on: July 12, 2003, 07:13:00 PM »
Benzene Hydrocarbons with a Pseudo Allyl Side Chain: Methovinylbenzene and its Homologues. Study of Certain Molecular Migrations. Second Part. Study of Molecular Transpositions which Accompany the Transformation of -Glycols and their Derivatives into Aldehydes and Ketones.
Tiffeneau, M.

Ann. chim. phys., [8], Vol 10, pp 322-78 (1908)

(https://www.thevespiary.org/rhodium/Rhodium/djvu/tiffeneau.carbures-benzenique.djvu)

Abstract

This paper consists of a continuation of the experimental study and theoretical consideration of certain migrations which take place in derivatives of glycols under the influence of various reagents.  It was previously observed (Ann. chim. phys. [8], 10, 145-98) that halohydrins of -glycols, when treated with alkalies and then distilled, gave first an oxide and then an aldehyde, thus but with AgNO3, or HgO a more deep-seated transformation took place, resulting in the migration of a hydrocarbon radicle. Thus, from the iodohydrin of methylphenylglycol, phenylacetone was obtained according to PhCOH(Me)CH2I PhCH2COMe. The author has studied successively the glycols, the oxides of ethylene and the halohydrins.

Among the -glycols he finds that the primary-secondary and primary-tertiary, after dehydration, rearrange themselves into aldehydes with only a shifting of the position of the hydrogen atom; for example, RCH(OH)CH2OH RCH=CHOH  RCH2COH; bi-secondary into ketones with only the migration of the hydrogen atom, e.g., MeCH(OH)CH(OH)Me MeCH2COMe, or into aldehyde, with wandering of the phenyl group, provided this group is attached to the carbon atom carrying hydroxyl, which does not enter into the dehydration, thus, MeCH=C(OH)Me and PhCH=C(OH)Me, isomerize without migration of hydrocarbon group. PhCH=C(OH)Ph isomerizes with migration of a hydrocarbon group.  In the case of the bi-tertiary the rearrangement cannot take place without a wandering of a hydrocarbon radicle.  All the oxides of ethylene, except the tetra-substituted derivatives, isomerize with the simple migration of the hydrogen atom.

In the case of the isomerization of iodohydrins of aromatic nature into aldehydes and ketones, the migration of the phenyl group takes place when it is attached in the hypothetical intermediate substance to the carbon carrying the hydroxyl group; the same is true of the magnesium derivatives of the halohydrins.

Experimental

Unsymmetrical methylphenylethyleneglycol, PhMeC(OH)CH2OH, can be made by the action of barium hydrate or carbonate in the presence of water on the dibromide of methovinylbenzene, or from methylmagnesium iodide and benzyl carbinol, m. 42-43°C, b26 160-162°C.  Heated with dilute H2SO4 it gives hydratropic aldehyde.  Unsym. methyl-p-tolylethyleneglycol, MeC6H4COHMeCH2OH, m. 36°C, b15 175-80°C, obtained in a similar manner to the preceding compound, by boiling with dil. H2SO4 gives methylhydratropic aldehyde, b730 219-221°C.  Unsym. diphenylethyleneglycol, Ph2C(OH)CH2OH, from phenyl magnesium bromide and ethyl glycollate, m. 122°C. Boiled with dil. H2SO4, it gives diphenylacetaldehyde, b15 170-175°C.  Symmetrical methylphenylglycol (See Fincke, Ber., 17, 710) gives phenylacetone.

The oxide of styrene shows a remarkable stability in the presence of hydrolytic agents, since it does not give phenylacetaldehyde with H2SO4 and HNO3 or AgNO3; the oxide of methylvinylbenzene, on the other hand, isomerizes very rapidly by heating with dil. H2SO4.

p-Methoxystyrolene, obtained by the method of Klages (Ber., 36, 3592) gives with mercuric oxide and iodine, methylphenylacetaldehyde, b. 255-256°C, d0 = 1.140, oxime, m. 121°C (Bouveault, Compt. rend., 135, 41), semicarbazone, m. 181-182°C.  On reduction with zinc and acetic acid, the aldehyde gives the acetate of p-methoxyphenylethanol, b11, 156-7°C, d0= 1.101.

Phenylpropylene, by passing through the intermediate iodohydrin, gives hydratropic aldehyde, whose oxime is a liquid, b7 124°C.  Reduced with zinc and acetic acid, the aldehyde gives the acetate of hydratropic alcohol, from which, by saponification, the alcohol may be obtained, b14 113-4°C.  Phenylmagnesium bromide, with the aldehyde, gives the alcohol PhCHMeCHOHPh.  From the iodohydrin of phenylpropylene one obtains phenyl-1-dimethylamino-2-propanol-1 (Fourneau, J. pharm. chim. [6], 20, 488), indicating the constitution of the iodohydrin.  Methyl-3-phenylbutylene, obtained by dehydration of the alcohol, PhCHOHC2CHMe2, gives isopropylphenylacetaldehyde, b. 215-220°C, semicarbazone, m. 140°C.  The iodohydrin of methylphenylglycol, PhMeCOHCH2I, gives phenylacetone.  This ketone with phenylmagnesium bromide gives ,-diphenylpropylene (Klages, Ber., 35, 2648).

n-Propylstyrolene, obtained from -propylcinnamic acid, which in turn was made from the ethyl ester, formed by the action of phenylbutanone in the presence of magnesium or ethyliodacetate, gives, through its iodohydrin, benzylpropylketone.  The n-propylstyrolene gives a liquid dibromide.

Diphenylmethylcarbinol, Ph2COHMe, m. 80-81°C (Tiffeneau, Bull. soc. chim. [3], 27, 292; Klages, Ber., 25, 2646; Masson, Compt. rend., 135, 533) by distillation at the ordinary temperature, gives the unsaturated hydrocarbon, Ph2CH=CH2, which, through its iodohydrin, yield desoxybenzoin.

p-Tolylphenylmethyl carbinol, MeC6H4(Ph)C(OH)Me, is obtained as liquid from p-methylacetophenone. By repeated distillation at ordinary temperatures, it gives p-tolylphenylethylene, b. 285-286°C, b6 145-146°C  The latter yields p-tolylacetophenone.  Phenyl-2-butylene, through its iodohydrin, gives methylbenzylmethyl ketone, PhCHMeCOMe, b. 210-212°C, b23, 106-107°C.

Phenyl-2-n-amylene, PhMeC=CHCH2Me, gives a ketone which does not combine with sodium sulphite, b. 225-227°C. Semicarbazone, m. 188°C.  Phenyl-3-n-amylene, PhC(Et)=CHMe, was made by dehydration of the diethylphenylcarbinol made by action of ethyl magnesium bromide on ethylbenzoate, b. 197-9°C, d0=0.9321.  Through the iodohydrin it gives methylbenzylethyl ketone, MePhCHCOEt, b. 222-225°C, d0=0.982.  Semicarbazone, m. 172°C.  By the action of ethyl magnesium bromide on chloracetophenone, benzylethylketone is formed, semicarbazone, m. 146°C.

GC_MS

  • Guest
Fincke ?
« Reply #5 on: July 14, 2003, 10:23:00 AM »
Symmetrical methylphenylglycol (See Fincke, Ber., 17, 710) gives phenylacetone

Fincke?  ;D

Ueber zwei isomere Phenylmethylglycole. I.
Th Zincke

Ber Deutsch chem Ges 17 (1884) 708-713

(https://www.thevespiary.org/rhodium/Rhodium/pdf/p2p.phenylpropanediol.pdf)


roger2003

  • Guest
Ber. 60, 1050 (1927)
« Reply #6 on: October 20, 2003, 06:38:00 PM »
From Ber. 60, 1050 (1927) the (I think) important steps:

In the first step they synthesice  alpha-metylstyrene IUPAC:  2-Phenylpropene , in the next step they converted this with 83% yield to the Oxid IUPAC:  2-Methyl-2-phenyl-oxirane

The Oxid was converted by Hydration ( with aqueous  HCl) to the corresponding Glykol (bad yield)  IUPAC: 2 Phenyl-propane-1,2-diol   

This Glykol was also synthesiced (with better yield) from Acetophenone.

With Oxid and Glykol than are following some isomerisations pp:

From Oxid
I.
The Oxid  (on clay) is distilled with  91% yield of Methyl-Phenyl-acetaldehyd ( = Aldehyd I)
II.
The Oxid on Pumice with 50%  H2SO4 is heated to 140-150°  with 64% yield of
( =Aldehyd I)
III.
The Oxid with H2SO4 at –15° C yields  46% BMK
  

From Glykol
I.
The Glykol under CO2 Steam  with 20% H2SO4 yields  80% Methyl-phenylacetaldehyd (=Aldehyd II)
II.
6 g Glykol ,12 g Oxalic Acid  and 6 ml H2O are (water bath) heated (under CO2 Steam) and the yield is 82% BMK
III.
50%  H2SO4  (50-55°)  unter CO2 Steam.  Aldehyd II und BMK with a ratio of 2:1
IV.
With H2SO4 at –15°  yield 48% BMK


Aldehyd I
I .
Yields with concentrated ( –16°)  H2SO4  48% BMK
III.
Yields with HgCl2  a Mixture from 90% Aldehyd and 10% BMK

Aldehyd II
II.
Yields with ( –16°) H2SO4 62% BMK
IV.
with HgCl2 80% BMK

They differ between Aldehyd I and Aldehyd II, but I think it`s Hydratopaldehyde with different impurities.

Rhodium

  • Guest
Mercury-free Iodohydrin Formation
« Reply #7 on: June 07, 2004, 12:14:00 AM »
As you can see in the articles above, both alpha-methyl-styrenes and allylbenzenes (like safrole) can be turned into their corresponding phenylacetones (P2P/MDP2P etc.) by making the iodohydrin followed by acid/base hydrolysis. Unfortunately the authors back then used iodine together with a huge amount of a mercury salt to prepare the iodohydrins, considerably lessening the convenience of this route. However, in the 100 years since the above articles were written, there has been considerable improvements made in the field of iodohydrin formation, and below I present the most important advances:



Iodohydrins and Epoxides from Olefins
J. W. Cornforth and D. T. Green

J. Chem. Soc. (C), 846-849 (1970)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/iodohydrin.hio3-i2.pdf)

Abstract
Reaction of olefins with iodine in the presence of water and a suitable oxidizing agent such as iodic acid, or oxygen catalysed by nitrous acid, gives iodohydrins. These form epoxides readily on treatment with bases.
____ ___ __ _

Acetoxyiodination of Olefins: A New Method for the Preparation of trans-Iodohydrin Acetates
Michelangelo Parrilli, Gaspare Barone, Matteo Adinolfi and Lorenzo Mangoni

Gazzetta Chimica Italiana 104, 835-842 (1974)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/alkene.acetoxyiodination.pdf)

Abstract
The reaction of 1-methyl-4-tert-butylcyclohexene and of 1-methylcyclohexene with I2 and KIO3 in AcOH has been shown to give mainly the acetoxy-iodides [Ib] and [IIb] and the acetoxy-iodides [IIIb] and [IVb], respectively. Therefore, it may be considered to be a new one-step method for the preparation of trans-iodohydrin acetates starting from olefins. Product distribution showed that in the first stage of the reaction the iodonium ions formation is reversible.
____ ___ __ _

An improved synthesis of iodohydrins from alkenes
M. Smietana, V. Gouverneur and C. Mioskowski

Tetrahedron Letters 41(2), 193-195 (2000)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/alkene2iodohydrin.nis.pdf)

Abstract
A series of iodohydrins was prepared in excellent yields in a one-step procedure by treating the corresponding alkenes at -20°C with NIS in aqueous DME.
____ ___ __ _

The procedure in the last article requires the quite expensive compound N-Iodosuccinimide (NIS), but that can be made in high yield from sodium iodide and NCS (and presumably NBS as well), see the following article:

N-Chlorosuccinimide/Sodium Iodide: A Convenient Source of N-Iodosuccinimide (NIS)
Synthesis of trans-1,2-Iodoacetates from Alkenes

Yashwant D. Vankar and G. Kumaravel

Tetrahedron Letters 25(2), 233-236 (1984)

(https://www.thevespiary.org/rhodium/Rhodium/chemistry/nis.alkene.iodoacetoxylation.html)

Abstract
Equimolar amounts of N-chlorosuccinimide and sodium iodide in acetone are found to be a convenient source of N-iodosuccinimide using which trans-1,2-iodoacetates and ?-iodo carbonyl compounds have been prepared from olefins and enol silyl ethers respectively.


jim

  • Guest
While on this subject...
« Reply #8 on: June 07, 2004, 09:12:00 PM »
You say that P2P can be made "... from 2-phenyl-1,2-propandiol..."  ?!  I think you meant to say  1-phenyl, 1,2-propandiol. 

But since you mentioned that P2P can be made from 1-phenyl, 1,2-propandiol let me just mention that a long time ago I posted an article that synthesized 1-phenyl, 1,2-propandiol  from benzaldehyde and yeast! 

use the search engine...

Rhodium

  • Guest
Both phenyl-1,2-propanediols will do!
« Reply #9 on: June 07, 2004, 09:33:00 PM »
Yes, P2P can be made by acid treatment of 1-phenyl-1,2-propanediol, but that is well known (as this corresponds to the isosafrole glycol intermediate gotten in the peracid oxidation of isosafrole).

The novel thing here is the re-discovery that 2-phenyl-1,2-propanediol (alpha-methyl-styrene glycol) will also give P2P under certain conditions. See the partial translation of the article I found in

Post 465776

(roger2003: "Ber. 60, 1050 (1927)", Novel Discourse)


From 2-Phenyl-propane-1,2-diol
I. The Glykol under CO2 Steam  with 20% H2SO4 yields  80% Methyl-phenylacetaldehyd (= Aldehyd II)
II. 6 g Glykol, 12 g Oxalic Acid  and 6 ml H2O are (water bath) heated (under CO2 Steam) and the yield is 82% BMK
III. 50%  H2SO4 (50-55°C)  unter CO2 Steam.  Aldehyd II und BMK with a ratio of 2:1
IV. With H2SO4 at –15°C yield 48% BMK