roger2003
(Hive Bee)
10-16-03 08:09
No 464984
      Hydratropaldehyde
(Rated as: excellent)
    

CAS [93-53-8]
Synonyms : 2-Phenyl propanal; 2-Phenylpropionaldehyde;  Alpha-methyl phenylacetaldehyde; Alpha-methyl tolualdehyde; Benzeneacetaldehyde, alpha-methyl-; Cumenealdehyde; Hydratropic aldehyde;


Hydratropaldehyde was discussed in The Hive :

Post 411744 (Rhodium: "New P2P syntheses from industrial chemicals", Novel Discourse):

Post 412032 (Rhodium: "hydratropaldehyde", Novel Discourse):

Post 427944 (lugh: "Hydratropaldehyde", Stimulants):

Post 464180 (lugh: "Hydratropaldehyde", Chemicals & Equipment):


In Rhodiums page you can find procedures to convert this compound to P2P

../rhodium /2-phenylpropanal.html

From Ullmann`s:

2-Phenylpropionaldehyde (hydratropaldehyde) has long been established in the fragrance industry. It occurs in many natural products and has a strong fruity smell, reminiscent of hyacinths. Surprisingly, 2-phenylpropanal is much less sensitive to oxidation and polymerization than 2-phenylacetaldehyde. For a review on 2-phenylpropanal and the corresponding alcohol, see Post 110 (not existing).

Production In the last few years a series of new syntheses for 2-phenylpropionaldehyde has been described. However, only a few have achieved industrial significance. The most important is the rhodium-catalyzed hydroformylation of styrene.
In this process [HCo(CO)4] is unsuitable as a catalyst because then styrene is largely hydrogenated [10], [11]. The use of chiral rhodium complexes leads to the formation of optically active aldehydes when prochiral olefins, such as styrene, are used. Asymmetric hydroformylation, however, has so far found no industrial application because of insufficient purity of the enantiomers [12].
Other synthetic methods are the gas-phase oxidation of a-methylstyrene on Cu, Bi – Mo – P – SiO2 [13], or Pd salt catalysts [14], the rearrangement of expoxidized a-methylstyrene [00][01][02][03], and the dehydrogenation of 2-phenyl-1-propanol on Ag catalysts at reaction temperatures of ca. 600 °C [05], [06].

Uses 2-Phenylpropanal and its hydrogenation product, 2-phenylpropanol, are used in perfumes. The aldehyde also is a valuable starting material for a series of pharmaceuticals and pesticides, and it serves in the plastics field as a stabilizer, catalyst, and hardener.


[ 1] J. Falbe (ed.): "Aldehyde," in Houben-Weyl: Methoden der Organischen Chemie, vol. E 3, Thieme Verlag, Stuttgart-New York 1983.
[10]  B. Cornils, R. Payer, Chem. Ztg. 98 (1974) 596 – 606.
[11]  H. Siegel, W. Himmele, Angew. Chem. 92 (1980) 182 – 187; Angew. Chem. Int. Ed. Engl. 19 (1980) 178.BASF Patent DE2132414, 1971 (W. Himmele, H. Siegel, W. Aquila, F. J. Mueller).Ethyl Corp., Patent US3907847, 1970 (K. A. Keblys).
[12]  J. M. Brown, Chem. Ind. (London) 1982, no. 10, 737. Agency of Ind. Sci. Technol., JP 7757108, 1975 (I. Ogata, M. Tanaka, Y. Ikeda, T. Hayashi). L. Marko in [1], p. 224 [1] .
[13]  I. L. Belostotskaya, G. A. Khmeleva, Termokatal. Metody Pererab. Uglevodorodnogo Syr'ya 1969, 221 – 224.
[14]  W. Hafner et al., Chem. Ber. 95 (1962) 1575.
[00]  Toyo Soda, JP 8218643, 1980 (Chem. Abstr. 97 (1982) 38670).
[01]  PCUK,  FR2338920 , 1976 (J. C. Volta, J. M.Cognion).
[02]  Ajinomoto, JP 242278, 1971 (Y. Matsuzawa, T. Yamashita, S. Ninagawa).
[03]  Cosden Technology, Patent DE2501341,, 1974 (J. Watson). = Patent US3972110
[05]  BASF, Patent EP0004881, 1978 (W. Sauer, W. Fliege, C. Dudeck, N. Petri).
[06]  Givaudan, FR2231650, 1973 (I. Huang, L. M.Polinski, K. K. Rao).
Patent US4154762



Other references:

Beilstein E IV 7, 695
Vogel 3rd p. 906
Common Fragrance and Flavor Materials Edition 2001 p. 104
Patent US3379768
Patent DE602816 = Patent US1899340

Patent DE1568350 = Patent US3452047

In this patent Anethol is converted in one step to the corresponding Hydratropaldehyde by Thallium(III) salt

This salt converts also in one step:

Styrene          --> Phenylacetaldehyde --> Benzaldehyde
alpha-methyl-stryrene -->  Benzyl-Methyl-Ketone

Wanted References

J. Falbe (ed.): "Aldehyde," in Houben-Weyl: Methoden der Organischen Chemie, vol. E 3, Thieme Verlag, Stuttgart-New York 1983 p. 224

B. Cornils, R. Payer, Chem. Ztg. 98 (1974) 596 – 606.

H. Siegel, W. Himmele, Angew. Chem. 92 (1980) 182 – 187

W. Hafner , Chem. Ber. 95 (1962) 1575.

I need also references about thallium, especially for converting Thallium(I)sulfate to Thallium(III)sulfate.
I know, it`s a poison
 
 
 
 
    Rhodium
(Chief Bee)
10-16-03 15:19
No 465050
      Aqueous Wacker + Phenylpropanal
(Rated as: excellent)
    

Über die Reaktionen von Olefinen mit wässrigen Lösungen von Palladiumsalzen
W. Hafner
Chem. Ber. 95, 1575-1581 (1962) (../rhodium/pdf /wacker.aqueous.pdf)

Phenylpropanale und Phenylpropanole - Aktuelle Schlüsselverbindungen
B. Cornils, R. Payer
Chem. Ztg. 98, 596–606 (1974) (../rhodium/pdf /phenylpropanale.phenylpropanole.pdf)

Synthesis of Intermediates by Rhodium-Catalyzed Hydroformylation
H. Siegel & W. Himmele
Angew. Chem. Int. Ed. Engl. 19, 178–183 (1980) (../rhodium/pdf /hydroformylation.rh-cat.pdf)
[ English translation of Angew. Chem. 92, 182–187 (1980) ]
 
 
 
 
    roger2003
(Hive Bee)
10-20-03 04:52
No 465749
      Hydratropaldehyde
(Rated as: good read)
    

Hydratropaldehyde (from alpha-methylstyrene) (with chromyl chloride)

Organic Syntheses CV 6, 1028 (http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?prep=CV6P1028)
Tetrahedron 25, 3441 (1969) (../rhodium/pdf /p2p.chromylchloride.pdf)

From Cumene and chromyl chloride
Ber 24, 1358 (1891)


For chromyl chloride see: Post 447723 (Rhodium: "If it Looks Like Bromine and Smells Like Bromine..", Novel Discourse)
 
 
 
 
    roger2003
(Hive Bee)
12-14-03 05:26
No 476771
      Hydratropaldehyde     

Hydratropaldehyde by Oxo Process from Styrene:

This was discussed:

Post 476493 (Rhodium: "Catalytic Hydratropic Aldehyde", Methods Discourse)
Post 476616 (roger2003: "Hydratropaldehyde", Methods Discourse)

and in "Ullmanns"

As shown , rhodium-based processes can be classified into three types. The most important of these on an industrial scale uses the so-called phosphine-modified catalyst system. The unmodified rhodium carbonyl complex is used for the reaction of special olefins.

Low-Pressure Oxo (LPO) Process. In the mid-1970s Union Carbide and Celanese succeeded in using rhodium – triphenylphosphine catalysts for the hydroformylation of olefins on an industrial scale. Since then some other companies have developed modifications of this process. The most important of these, however, is the low-pressure oxo (LPO) process jointly developed by Union Carbide, Davy McKee, and Johnson Matthey. A detailed description of this specific low-pressure route follows with the conversion of propene to butyraldehyde as an example.
Figure (5) shows a schematic of hydroformylation with the LPO gas-recycle process [8], [36].
The reaction takes place in a stirred-tank reactor made of stainless steel. The reactants and supplementary catalyst to make up for catalyst lost in production are fed in from below. Due to the sensitivity of the rhodium catalyst system toward catalyst poisons, the olefin and synthesis gas or hydrogen used as makeup gas must first be carefully purified . The reactor contains the catalyst dissolved in high-boiling reaction byproducts. In order to maintain catalyst activity a portion of the solution must be continuously removed and reprocessed separately , and the noble metal and the phosphine returned to the process. From time to time, all of the catalyst must be removed via line  and reprocessed externally [12] , [16]. The hydroformylation reaction takes place at < 20 bar and 85 – 115 °C. The reactor jacket is cooled to remove the heat of reaction. The reaction products and unreacted gaseous reactants (conversion of about 30 % per pass) are forced out of the reactor by the recycled gas and pass through the demister and the condenser into the separator
Unreacted starting materials and part of the propane formed as byproduct are recycled to the reactor by means of the compressor. The level of propane in the circulating gas is adjusted by means of the outlet . The liquid reaction products are freed from residual olefin in a stripping column , and are worked up by multistage distillation. Residual olefin from the stripping column is recycled. To limit the buildup of inerts in the recycled gas stream and to reduce losses by venting, other treatment steps may be applied. These include extraction of propene with the aldehyde products, stripping the olefin from the aldehydes with synthesis gas and recycling both to the reactor [55], and washing the off-gas with stripped catalyst solution [56].
The LPO gas-recycle process has been partly replaced by a liquid-recycle variant, in which the catalyst solution and the aldehyde products leave the reactor as a liquid. The catalyst solution is separated from the aldehydes in several distillation steps and recycled. Combinations of gas and liquid recycle have also been described and are claimed to give increased propene conversion [53], [54].

Ruhrchemie – Rhône-Poulenc (RCH – RP) Process. Another industrial low-pressure process for olefin hydroformylation is based on a water-soluble rhodium catalyst [37][38][39][40][41][42][43]. As with the LPO process, the RCH – RP process has found its greatest importance in the hydroformylation of propene.
The use of a water-soluble catalyst system is associated with substantial advantages for industrial practice, because the catalyst can be considered to be heterogeneous. Since the catalyst is insoluble in the organic phase formed, separation of the aqueous catalyst phase and the butanal is greatly simplified by phase separation, and losses of the noble metal in the crude aldehyde stream are negligible. High-boiling byproducts do not dissolve in the aqueous catalyst phase, dispensing with the need for continuous catalyst regeneration. In the LPO process, however, these byproducts are retained in the catalyst phase and lead to catalyst problems, unless the catalyst system is continuously regenerated.
The process is explained by means of the simplified flow sheet . The reaction takes place in a stirred-tank reactor , which contains the catalyst solution; the reactants are introduced from below. Before entering the reactor, the synthesis gas is first passed through a stripping column  in countercurrent to the crude aldehyde stream in order to recover the unreacted propene. Furthermore, purification of the reactants can be avoided by this procedure [42]. The crude aldehyde product leaves the top of the reactor and passes through the trap  into the phase separator  where it is separated from the entrained catalyst solution. The catalyst solution is returned to the reactor via the heat exchanger .
Because of the higher temperature compared to the LPO process , the heat of reaction can be used for steam generation in the heat exchanger . The crude aldehyde from the phase separator is distilled. Part of the water is retained in the crude aldehyde in homogeneous solution. This loss of water is compensated for via inlet . Part of the off-gas which escapes via the separator  can be recirculated; part must be drawn off to maintain a constant propane level in the gas. Depending on the purity of the olefin used, the off-gas  may contain considerable amounts of olefin. The RCH – RP process may then, for example, be combined with a cobalt high-pressure process to convert the residual olefin [44].

Rhodium High-Pressure Process. If unmodified rhodium carbonyl hydride is used as a hydroformylation catalyst, the reaction product consists of roughly equal amounts of branched and straight-chain aldehydes . For this reason this catalyst is only applicable if the n/i ratio is not important (i.e., both aldehydes are valuable products) or if the formation of a branched aldehyde is impossible (e.g., in the hydroformylation of ethylene to give propanal) [45]. Anhydrous propanal can be obtained by this process.


[8]  Winnacker-Küchler 4th ed., 5, 537.
[36]  F. Heinrich, M. Bernard, 27th DGMK-Haupttagung, Aachen Oct. 6 – 8, 1982, Compendium 82/83, p. 189.
[12]  P. E. Garrou, Chem. Rev. 85 (1985) no. 3, 171.
[16]  P. E. Garrou, R. A. Dubois, W. J. Chu, CHEMTECH 1985, no. 2, 123.
[55]  Union Carbide Chemicals and Plastics Company, Patent EP048976 , 1991 (K. D. Sorensen).
[56]  Union Carbide Chemicals and Plastics Company, Patent EP0404193, 1991 (D. L. Bunning).
[53]  Union Carbide,Patent EP0188246, 1986 (D. L. Bunning, M. A. Blessing).
[54]  Davy Powergas, Patent GB1387657, 1973 (R. Fowler).
[37]  Rhône-Poulence Industries, Patent DE2627354, 1976 (E. Kuntz).
[38]  Rhône-Poulenc Chimie de Base, Patent EP0104967 B 1, 1982 (J. L. Sabot).
[39]  Rhône-Poulenc Recherches, Patent EP0133410 A 1, 1984 (J. Jenck, D. Morel).
[40]  Rhône-Poulenc Recherches, Patent EP0158572 A 1, 1985 (C. Barre, M. Desbois, J. Nouvel).
[41]  Rhône-Poulenc Industries, FR 8 005 488, 1980 (J. Jenck).
[42]  Ruhrchemie AG, Patent EP0103810, 1983 (B. Cornils et al.).
[43]  Ruhrchemie AG, Patent EP0158246 A2, 1985 (B. Cornils et al.).
[44]  Ruhrchemie AG, Patent EP0111257B 1, 1983 (B. Cornils et al.).
[45]  Ullmann, 4th ed., 19, 443.

roger2003
 
 
 
 
    java
(Hive Bee)
12-19-03 10:02
No 477862
      RE: Hydratropic aldehyde.;.....     

I was looking at Ibuprofen  the other day , and it sure looks like a good candidate for a substituded Hydratropaldehyde once the COO is reduced to COH. What I'm not sure about is the effect of the four carbon chain attached on the benzene ring..........java

We're  all in this world together,
http://www.aztlan.net
 
 
 
 
    roger2003
(Hive Bee)
12-28-03 06:39
No 479468
      Hydratropic aldehyde dimethyl acetal
(Rated as: good read)
    

Hydratropic aldehyde dimethyl acetal
CAS 90-87-9


Patent US3257298   from alpha-methylstyrene in a single electrolytical step

The electrolysis cell ( platinum anode and a carbon cathode) was divided with an alundum membrane, The anode chamber was filled with 180 ccm of a solution, prepared by mixing 10 g of alpha-methylstyrene with 20 ccm of 0,2 N aqueous solution of lithium chloride  and than making up the mixture to a volume of 500 ccm with a solution of 0,2 N lithium chloride in MeOH

The cathode chamber was filled with a 0,2 N solution of lithium chloride in MeOH

A direct current of about 0,8 A and about 7-8 V are passed through the cell for about 6 hours.
at 65° C

Yield 9 g from 2 runs (bp 64-66° at 1 mm)

.