Author Topic: Chem. Abs. 130:24638.  (Read 5231 times)

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Rhodium

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Chem. Abs. 130:24638.
« on: June 20, 2003, 05:30:00 PM »
Study on polymer-supported bromate ion oxidizer with sodium bisulfate    
Yang, Guichan; Chen, Zuxing; Shi, Congyun   
Hubei Daxue Xuebao, Ziran Kexueban 20(3),  256-259 (1998)
ISSN: 1000-2375 - CAN 130:24638   

Abstract

Polymer-supported bromate ion oxidizer was prepared from strong basic ion-exchange resin with sodium bromate.  The primary alcohols and simple ethers were effectly oxidized to esters, secondary alcohols to ketones, ,-diols and cyclic ether to lactone, thiol and selenol to disulfide and diselenide in the presence of sodium bisulfite with polymer-supported bromate ion oxidizer.  Higher yields were obtained.

Rhodium

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Chem. Abs. 130:313445
« Reply #1 on: June 20, 2003, 05:32:00 PM »
Study on polymer-supported tribromide oxidizing agent    
Yang, Guichun; Chen, Zuxing; Zhang, Shengli; Chen, Jiawei   
Lizi Jiaohuan Yu Xifu  (1998),  14(6),  475-480. 
ISSN: 1001-5493 - CAN 130:313445

Abstract

Polymer-supported tribromide oxidizing agent was prepared by 717# strong base ion exchange resin and elemental bromine. The quantity of the polymer-supported tribromide oxidizing agent was detd.  Primary alcohols and simple ethers were oxidized to esters, benzyl alcohol to benzaldehyde, second alcohols to ketones, and ,-diols and cyclic ethers to lactones by the polymer-supported tribromide oxidizing agent. The oxidized products were confirmed by IR and 1H-NMR, and good yields were obtained.

Rhodium

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1,4-Butanediol to gamma-Butyrolactone in French
« Reply #2 on: June 22, 2003, 08:33:00 PM »

Tetrahedron Letters, 22(41), 4073-4076 (1981)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.cuo.pdf) details the catalytic dehydrogenation of 1,4-Butanediol to gamma-Butyrolactone (95% conversion, 80% yield) by nothing else than heating the diol to 200°C for 15h with a small amount (0.01 mol%) of Copper(II)oxide (CuO), but unfortunately this article is written in French...

Could we please have this translated to English?

Rhodium

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1,4-BD -> GBL (92%) using NaBrO2/Alumina
« Reply #3 on: June 27, 2003, 02:20:00 AM »
Oxidation of 1,4-Butanediol to gamma-Butyrolactone using Sodium Bromite Trihydrate and Alumina

Chemistry Letters, pp 53-54 (1994)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bdo2gbl.bromite-alumina.pdf)

NaBrO2.3H2O/Alumina oxidation of 1,4-Butanediol to gamma-Butyrolactone in 92% yield. (Could somebody type the article and post in this thread, please?)

Vitus_Verdegast

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article typed up
« Reply #4 on: June 29, 2003, 04:46:00 PM »
CHEMISTRY LETTERS pp. 53-54, 1994

Oxidation of diols with Sodium Bromite Trihydrate in Organic Solvents in the presence of Alumina

Takashi MORIMOTO, Masao HIRANO, Keiko IWASAKI, and Takashi ISHIKAWA

The title oxidation of diols with two primary hydroxy groups (symmetrical diols) and those with both a primary and a secondary hydroxy group (unsymmetrical diols) gives the corresponding lactones or the hydroxy ketones, being dependent upon the types of diols.



Sodium bromite trihydrate 1 (referred to simply as NaBrO2) is a versatile reagent for the oxidative transformation of many classes of organic compounds1 inclusive of diols2 in aqueous media, but its behavior in a water-free solvent has not been fully studied3. In the course of the work aiming at the oxidation of various functional groups with 1 in aprotic solvents, succesful conversion of diols to the corresponding lactones and/or the hydroxy ketones was found in dichloromethane (DM) or acetonitrile (AN) with the aid of alumina under mild conditions.4

Thus various symmetrical 1,4- and 1,5-diols were treated with the NaBrO2/alumina system in DM at room temperature under anaerobic conditions, giving the five- and six-membered lactones, respectively, in fair yields; the following examples are representative.



The oxidation of unsymmetrical 1,4- and 1,5-diols did not give the hydroxy ketones, but "abnormally" led to lactones (Table 1): use of AN instead of DM allows the reaction time of a diol with a long alkyl-chain to be lessened considerably without affecting the course of the reaction. This unexpected lactone formation is of special interest, because this phenomenon is markedly contrast to that observed in the conventional oxidation in aqueous medium2, in which secondary hydroxy group was "normally" oxidized in preference to primary one, giving the hydroxy ketone exclusively. Hence, the oxidation of various types of diols was then attempted.


PhCH(OH)CH2OH  --->   PhC(=O)CH2OH    70%

HOCH2CH(OH)C6H14   --->   HOCH2C(=O)C6H14    76%

HO(CH2)2CH(OH)Me   --->   HO(CH2)2C(=O)Me    65%







The oxidation of 1,2-diols gave the hydroxy ketones without concurrent carbon-carbon fission as shown above, while the lactones were absent. Similarly, selective formation of the hydroxy ketones from 1,3-diols was observed as typically exemplified by butane-1,3-diol (vide supra). On the other hand, neither a primary nor a secondary hydroxy group was selectively oxidized in the case of 1,6-diols; viz. hexane-1,6-diol gave a complex mixture containing the corresponding epsilon-lactone (max. 38% by GLC) and heptane-1,6-diol gave both 2-methyl-epsilon-lactone (56%) and the hydroxy ketone (44%). Thus, these diols showed the intermediate properties between those of 1,4- and 1,5-diols and 1,2- and 1,3-diols.

Although mechanistic approach is beyond this article, the varying results with the types of diols, especially the tabulated lactone formation, appears to be related to heterogeneous milieu, that is, to the stereochemistry of an absorbed diol on the alumina surface, since 1 is insoluble in DM and no perceptible reaction takes place without alumina. Accordingly, alumina plays important roles not only in increasing the active surface of a given amount of 1, but in determining reactivity of a diol and selectivity of a product.


References.

1. T. Kageyama, Y. Ueno and M. Okawara, Synthesis, 1981, 815;
   M. Okawara, Yuki Gosei Kagaku Kyokai Shi. 42, 751 (1984)

2. T. Kageyama, S. Kuwahara, K. Kitahara, Y. Ueno and M. Okawara, Chem. Lett. 1983, 1097

3. T. Kageyama and T. Yamamoto, Chem. Lett., 1980, 671;
   idem. Makromol. Chem. 182, 705 (1981)

4. The present oxidation procedure using commercial dry alumina (ICN BIOCHEMICALS Alumina A. Super I) is very simple and almost the same as that shown previously; M. Hirano, M. Oose, and T. Morimoto, Chem. Lett., 1991, 331;
   idem. Bull. Soc. Chim. Jpn. 64, 1046 (1991)


Rhodium

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BDO to GBL w/ NaOCl/RuCl3 (Conv 83%, Select 97%)
« Reply #5 on: July 03, 2003, 07:19:00 PM »
Production of -butyrolactone by liquid phase oxidation of 1,4-butanediol
Mukhopadhyay S., Chandalia S.B.,

Indian J. Chem. Technol., Vol. 6, No. 4, 237–239 (1999)

(https://www.thevespiary.org/rhodium/Rhodium/djvu/miukhopadhyay.djvu)

Abstract
An alternative manufacturing process-scheme was developed to synthesize gamma-butyrolactone with very high selectivity. Ruthenium trichloride was used as a redox catalyst and sodium hypochlorite as the oxidizing agent. Different process parameters such as temperature, effect of pH, mode of reaction and catalyst loading were studied to develop the most suitable process conditions. Under best suitable conditions, at 83% conversion level of 1,4-butanediol, 97% selectivity to the desired lactone was achieved in 5 h.

This reference was kindly retrieved by lugh, now can somebody please type and post it in this thread? A DjVu plugin can be downloaded from

http://www.lizardtech.com/download

if you don't have one already.

OcoteaCymbarum

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Industrial production of gbl
« Reply #6 on: July 12, 2003, 04:55:00 PM »
4. Production

Dehydrogenation of 1,4-Butanediol [110-63-4] (® Butanediols, Butenediol, and Butynediol). The Reppe process for manufacturing butyrolactone involves the endothermic dehydrogenation of 1,4-butanediol in the gas phase. This process is used by BASF, ISP, and Lyondell.
Preheated 1,4-butanediol vapor is introduced into a hot stream of circulating hydrogen and passed at atmospheric pressure through a bed of copper catalyst at temperatures between 180 and 240 °C (Figure (1)). The yield of butyrolactone is approximately 95 %. The reaction takes place via g-hydroxybutyraldehyde [25714-71-0] [7].
The byproduct hydrogen off-gas requires only simple purification before reuse (e.g., catalytic methanization of carbon monoxide impurities). The crude butyrolactone separated from the recycle gas stream contains small amounts of byproducts, including 1,4-butanediol, butyric acid, and high boilers, from which butyrolactone is separated by distillation.
Butyrolactone itself is noncorrosive and can be handled in carbon steel apparatus. However, where parts of the synthesis or distillation vessels and pipes come into contact with hot crude product containing butyric acid, they must be made of stainless steel.

Hydrogenation of Maleic Anhydride [108-31-6]. In the preparation of butyrolactone by hydrogenating maleic anhydride, molten maleic anhydride is fed into a preheated circulating stream of hydrogen and passed under a pressure of 6 – 12 MPa at 160 – 280 °C over a nickel-containing catalyst [8].
The reaction takes place via succinic anhydride [108-30-5] and can, by choice of the conditions, be continued to produce tetrahydrofuran [109-99-9]. The excess hydrogen is washed with water and recycled to the synthesis. Byproducts contained in the butyrolactone are separated out of the circulating gas: propanol [71-23-8], butanol [71-36-3], propionic acid [79-09-4], and butyric acid [107-92-6]. The butyrolactone is separated from these by distillation.
Because of the acids present, both the synthesis apparatus and the distillation apparatus must be made of stainless steel. The Japanese manufacturer Mitsubishi Chemical Corporation [9] uses this process.

Hydrogenation of Maleic Esters. New processes for the production of 1,4-butanediol and tetrahydrofuran starting from maleic anhydride via dimethyl maleate have been developed in the past few years (® Tetrahydofuran). They offer the possibility of extracting butyrolactone, which is an intermediate in these processes.
In a process developed by Kvaerner Process Technology (KPT, London) [10] dimethyl maleate [624-48-6] is produced in a first step from maleic anhydride and methanol with a strongly acidic ion exchanger as catalyst. The resulting dimethyl maleate is hydrogenated in the gas phase on a Cu-containing catalyst at a pressure of 2 – 8 MPa at 150 – 250 °C and gives a mixture of 1,4-butanediol, tetrahydrofuran, butyrolactone, and a small amount of the intermediate dimethyl succinate [106-65-0].
Butyrolactone and dimethyl succinate can be recovered as an azeotrope and recycled to the hydrogenation stage to obtain complete conversion to 1,4-butanediol and tetrahydrofuran. Alternatively the azeotrope can be refined by distillation to recover pure butyrolactone. The amount of butyrolactone depends on the pressure and temperature in the hydrogenation step, which influence the equilibrium between 1,4-butanediol and butyrolactone. Under the conditions described above it may vary from 5 to 50 %.
The new process has been licensed by KPT several times. The first commercial plants using this process are expected to come on stream in 2000.
A proprietary process practised by Eurodiol, a Belgian company of the SISAS group also starts from dimethyl maleate, which is hydrogenated in the gas phase at 1 – 2 MPa to give a mixture of butyrolactone and tetrahydrofuran in variable proportions. Butyrolactone and tetrahydrofuran are recovered as pure products by distillation, while the byproduct azeotrope butyrolactone/dimethyl succinate can be recycled for full conversion to butyrolactone and tetrahydrofuran or hydrogenated in a subsequent hydrogenation step in the liquid phase to give 1,4-butanediol and additional tetrahydrofuran.

Other Processes. Processes via tetrahydrofuran [11], dihydrofuran [12], acetylene [13], [14], butynediol [15],  olefins [16][17][18], butadiene  [8], or by carbonylation [19][20][21] are not industrially important.
Producers.
Butyrolactone is manufactured by BASF (Ludwigshafen, Germany and Geismar, USA), ISP (Calvert City and Texas City, USA), Lyondell (Channelview, USA), MCC (Mizushima, Japan) and Eurodiol (Feluy, Belgium).


[7]  S. Oka, Bull. Chem. Soc. Jpn. 35 (1962) 986 – 989.
[8]  Mitsubishi Petrochemical, DE-OS 1593073, 1966; DE-OS 1901870, 1969 (T. Asano, J. Kanetaka).
[9]  J. Kanetaka, T. Asano, S. Masumune, Ind. Eng. Chem. 62 (1970) 24 – 32. T. Yoshimura, Chem. Eng. N.Y. 76 (11. Aug. 1969) 70 – 72; Chem. Week 104 (1969) 63 – 72. S. Minoda, M. Miyajima, Hydrocarbon Process. 49 (1970) no. 11, 176 – 178.
[10]  M. W. M. Tuck, M. A. Wood, C. Rathmell, P. H. E. Eastland: "Butane to Butanediol: The emergence of a new Process Route," AIChE 1994 Spring International Meeting.
[11]  Quaker Oats, US 3074964, 1961 (A. P. Dunlop, E. Sherman).H. Hara, JP-Kokai 7887347, 1978.
[12]  BASF, DE 4 339 269, 1993 (R. Pinkos, R. Fischer).
[13]  BASF, WO 9 707 111, 1995 (M. Heider et al.).
[14]  BASF, DE 19 530 549, 1995 (M. Heider, T. Ruehl, J. Henkelmann, S. Stutz).
[15]  Y. Shvo, Y. Blum, J. Organomet. Chem. 238 (1982) C 79 – C 81.
[16]  Toa Nenryo Kogyo K.K., JP-Kokai 75 154 237, 1975 (Y. Okumura, Y. Nagashima).
[17]  Nat. Dist. and Chem. Corp., US 4 247 467, 1978 (J. H. Murib).
[18]  Standard Oil, US 4 238 357, 1980 (Th. Haase, F. A. Pesa).
[19]  Texaco, US 3 061 614, 1958 (W. M. Sweeney, J. A. Patterson).
[20]  The British Petroleum Company, EP 176 370, 1984 (H. Alper, D. J. H. Smith).
[21]  ARCO Chem. Technology LP, US 5 401 857, 1994 (D. Armstead, R. A. Grey).

Taken from Ullman's Encyclopedia of industrial chemistry

Rhodium

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Reduction of Succinic Anhydride to GBL
« Reply #7 on: October 23, 2003, 11:37:00 AM »
A Novel Production of -Butyrolactone Catalyzed by Ruthenium Complexes
Y. Hara, H. Kusaka, H. Inagaki, K. Takahashi, K. Wada

Journal of Catalysis, 194(2), 188-197 (2000)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/gbl.succinic.anhydride-ru-cat.pdf)
DOI:

10.1006/jcat.2000.2945



Abstract
-Butyrolactone (hereafter abbreviated GBL) is produced by the two-stage hydrogenation of maleic anhydride (MAH) in the liquid phase: the hydrogenation of MAH to succinic anhydride (SAH) in the first stage and the subsequent hydrogenation of SAH to GBL in the second stage. The latter hydrogenation has been studied using a homogenous catalyst. A novel ruthenium catalyst system consisting of Ru(acac)3, trioctylphosphine, and p-toluenesulfonic acid (p-TsOH) was developed for hydrogenating the SAH, which exhibited excellent catalytic performance, exceeding 95% selectivity for GBL and higher activity than that reported in the literature. It was found that p-TsOH plays an important role not only in enhancing the reaction rate, but also in improving selectivity. p-TsOH induces a structual change in the Ru complexes, leading to the cationic change which shows higher catalyst activity. It also prevents the undesired side reaction catalyzed by free trioctylphosphine thus resulting in high selectivity for GBL. A process to produce GBL was investigated. Some novel features of this process include the external preparation method of the Ru complex, the coupling reaction, and the separation to remove H2O, a product of hydrogenation of SAH, to increase the reaction rate. A catalyst recovery system was also developed to recover over 90% of the catalyst.



Succinic Anhydride -> GBL + THF
Catalyst:      Hydrous zirconium oxide (IPA, 280°C)
Subject Studied:   Product distribution
Takahashi, Kyoko; Shibagaki, Makoto; Matsushita, Hajime; Bull.Chem.Soc.Jpn. 65(1), 262-266 (1992)

Succinic Anhydride -> GBL
Reagent: Lithium borohydride (THF, 25°C, 15 min, 68%)
Narasimhan, Srinivasan Heterocycles 18, 131-135 (1982)

Succinic Anhydride -> GBL
Reagent: Na/Hg, HCl(aq)
Fichter; Herbrand; Chem. Ber. 29, 1193 (1896)

Rhodium

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1,4-BD -> GBL (4.5h, 84%) Electrooxidation
« Reply #8 on: March 14, 2004, 12:57:00 PM »
An aqueous silica gel disperse electrolysis system. N-Oxyl-mediated electrooxidation of alcohols
Hideo Tanaka, Yusuke Kawakami, Kentaro Goto and Manabu Kuroboshi

Tetrahedron Letters 42(3), 445-448 (2001)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bdo2gbl.electrooxidation.pdf)
DOI:

10.1016/S0040-4039(00)01979-1



Abstract
N-Oxyl-mediated electrooxidation of alcohols was performed in an aqueous silica gel disperse system. The newly devised electrolysis system offers an organic solvent-free and operationally simple procedure for oxidation of alcohols and could be successfully applied to kinetic resolution of sec-alcohol as well as enantioselective oxidation of meso-1,4-diol affording optically active gamma-lactone.




References

[1]
(a) Semmelhack, M. F.; Chou, C. S.; Cortes, D. A. J. Am. Chem. Soc. 1983, 105, 4492.
(b) Bobbit, J. M.; Hung, Q. T.; Ma, Z. J. Org. Chem. 1993, 58, 4837.
(c) Yanagisawa, Y.; Kashiwagi, Y.; Kurashima, F.; Anzai, J.; Osa, T.; Bobbit, J. M. Chem. Lett. 1996, 1043.
(d) Kashiwagi, Y.; Yanagisawa, Y.; Kurashima, F.; Anzai, J.; Osa, T.; Bobbit, J. M. J. Chem. Soc., Chem. Commun. 1996, 2745.
(e) Kashiwagi, Y.; Yanagisawa, Y.; Kurashima, F.; Anzai, J; Osa, T. Tetrahedron Lett. 1999, 40, 6469.
[2]
(a) Inokuchi, T.; Matsumoto, S.; Nishiyama, T.; Torii, S.

J. Org. Chem. 55, 462 (1990)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/electrooxidation.ref4.pdf)
(b) Torii, S.; Inokuchi, T.; Matsumoto, S.; Saeki, T.; Oki, T. Bull. Chem. Soc. Jpn. 1990, 63, 852.
(c) Inokuchi, T.; Matsumoto, S.; Torii, S.

J. Org. Chem. 1991, 56, 2416 (1991)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/electrooxidation.ref3.pdf)
(d) Inokuchi, T.; Liu, P.; Torii, S. Chem. Lett. 1994, 1411.
(e) Kuroboshi, M.; Yoshihisa, H.; Cortona, M. N.; Kawakami, Y.; Gao, Z.; Tanaka, H. Tetrahedron Lett. 2000, 41, 8131–8135.
[3] Involving HO(CH2)4CO2(CH2)4CO2H, HO2C(CH2)4CO2(CH2)5OH, etc.
[4] S.D. Rychnovsky, T.L. McLernon and H. Rajapakse.

J. Org. Chem. 61, 1194 (1996)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/electrooxidation.ref2.pdf)
[5] Determined by HPLC, column: CHIRALCEL-OD (4.6x50 mm), mobile phase: hexane/2-propanol (90/1), flow rate: 0.5 ml min-1.
[6] T. Ishikawa, Y. Oku and K.-I. Kotake.

Tetrahedron 53, 14915–14928 (1997)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/electrooxidation.ref1.pdf)


Rhodium

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GBL from 1,4-Butanediol using N-Haloamides
« Reply #9 on: April 14, 2004, 12:00:00 PM »
Convenient Synthesis of Lactones by the Reaction of Diols with N-Haloamides
Shuji Kondo, Shinya Kawasoe, Hideo Kunisada, and Yasuo Yuki

Synthetic Communications, 25(5), 719-724 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.haloamides.pdf)

Abstract
Reaction of 1,4-butanediol or 1,5-pentanediol with N-haloamides such as N-chlorosuccinimide, N-bromosuccinimide, N-bromoacetamide, isocyanuric chloride, and N,N-dichlorobenzenesulfonamide under mild conditions gave -butyrolactone or -valerolactone, respectively, in high yields.
____ ___ __ _

Preparation of N-Bromo-Acetamide from Acetamide and elemental Bromine

Organic Syntheses, CV 4, 104

(http://www.orgsyn.org/orgsyn/prep.asp?prep=cv4p0104)


ning

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Ning would like to mention that
« Reply #10 on: April 15, 2004, 08:28:00 PM »
In the "Mechanism and Synthetic Utility of the Oxidative Cleavage of Ethers by Aqueous Bromine" paper (JACS 1967,3350), where they get a (claimed) quantitative yield of GBL from THF using a 4x excess of bromine, in the penultimate paragraph, they mention that chlorine quantitatively broke ethyl ether into acetic acid. Which is exactly what the bromine did.

It seems to ning that the secret to the oxidation of THF with halogen agents is:

1. Time...there is a competitive halogenation reaction at work, but it's slower than the oxidation. Also, the lactone formed by oxidation is deactivated, but it will still oxidize too. Figure out a good reaction time and as soon as the reaction finishes, quench it! (Above paper: One day)

2. Darkness. Free radicals --> baaad. Ionic attack --> good. Wrap your beaker with tin foil. We don't like halogenated lactones. The above paper did this, and they claim quantitative yields of lactone. Let's follow their example.

3. pH control. Bleach, chloramines, halogens and water have such complicated interactions. pH is an essential controlling factor in determining what species are at work in solution. The above paper uses acetate buffer. Chloramines like TCCA have the handy advantage of eating their own HX acid to produce more HOX. pH 5 is what they used for bromine. I think chlorine's curve is one or two pH lower than bromine, so that would bee about pH 4 for bleach or TCCA.

4. Water! It seems obvious, but that extra oxygen, where does it come from? Water! I think I just saw a paper where they reacted 50 g of THF with TCCA, but it only contained 6 g of water! And they got a low yield of GBL. What a surprise!

5. Water! Don't use an alcohol as a solvent unless you want to waste large quantities of oxidizer. If it reacts with an ether, you can be damn sure it will attack alcohols. Acetone will work as a cosolvent, as long as you don't mind a few percent chloroacetone in your workup. On the other hand, this could be to your advantage, as the acetone or MEK could perhaps sponge up the chlorine radicals that would otherwise attach themselves to your desired product. But THF is pretty soluble in water already, right?

So ning's suggested procedure, not knowing the real way of light, would be:

1 mole THF (72g) mixed with 50 ml water to eat peroxides
1.2 moles Ca(OCl)2 (172g)

Dissolve the Ca(OCl)2 into 800 ml water stirred at room temp in big-ass flask wrapped with aluminum foil. Acidify to pH 4-5 or so with acetic acid (or HCl?), then mount a dropping funnel on top with the THF and start dripping the THF, keeping the temperature down. When the addition's done, let it stir for a few hours until the flask is completely cool. Then quench the reaction with something (bisulfite?) and extract however you like. I guess I'd use steam distillation, since that'd probably not take anything but the good stuff over, and the dum water would have to be removed anyway. Dare I hope for 86 g of lactone? Probably a regular distillation would have to bee performed just in case those dirty chlorinated lactones make it over too.

Thoughts?


armageddon

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1,4-BDO, THF and GBL from maleic dimethyl ester
« Reply #11 on: July 25, 2004, 03:11:00 PM »
Hi!

This is a dissertation about the catalytic gas-phase oxidation of maleic acid dimethyl esters on CuO-catalyst, and seems to be essentially the same like described a few posts earlier by OcoteaCymbarum (

Post 446714

(OcoteaCymbarum: "Industrial production of gbl", Methods Discourse)
, but of course A BIT more verbose (127 pages  :P ) - and unfortunately it is in german...

Here's a translation of part of the introduction:

"Gasphasenhydrierung von Maleinsaeuredimethylester zu 1,4-Butandiol, gamma-Butyrolacton und Tetrahydrofuran an Kupfer-Katalysatoren

(dissertation for the graduation to academical degree "Doctor of Science", by J.H. Schlander, University of Karlsruhe

{translation begin}
It is the goal of the present work to place a corner stone in systematic analysis of the multiple-stage gas phase hydration of maleic acid dimethyl esters on copper catalysts. To accomplish this, it was necessary to design and build a pilot plant which allowed for kinetic measurements inside a integral driven tube reactor.

With activated Cu/ZnO catalyst (selected based on orientating measurements) the product diversification is identified as function of the following parameters: pressure, temperature and reaction time.

Besides of maleic acid dimethyl esters, the intermediate products succinic acid dimethyl ester, GBL and 1,4-BDO were also used as starting compounds. The goal of the measurements is to help understanding the process of gas phase hydration of maleic acid dimethyl ester. Furthermore the measurements give information about how far the thermodynamic equilibrium between GBL and 1,4-BDO affects the ratio of these substances in the product stream.

Based on this data, it is shown that the system, based on a reaction matrix, can be described quantitatively with the help of simple basic kinetic approach.

Finally, a further development of the catalysts with regard to enhanced activity while maintaining same or better selectivity regarding value products is accomplished.
{translation end}


Very interesting, but unfortunately the text is >120 pages - else I would've translated the whole lot.. :P

I uploaded the PDF, for the interested amongst us....




Greetz A


armageddon

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1,4-BDO to GBL with hypochlorite?
« Reply #12 on: August 06, 2004, 12:53:00 PM »

https://www.thevespiary.org/rhodium/Rhodium/pdf/alcohols2methyl-esters.hypochlorite.pdf




I had the idea that the mentioned article could be useful when it comes to converting BDO to GHB - but I'm a bit unsure: the product from oxidizing 1,4-butanediol, 4-methyl-hydroxybutanoate, looks more like it could result in valerolactone - or is it already active by itself?

Is there a convenient way of removing the methyl? - Then this could well become a winner!!! (simple H2O hydrolysis maybe? ethylformate dissociates into EtOH and HCOOH upon prolonged contact with water, for example..)


BTW if double oxidation (at both OHs) was the main reaction to occur, then this would give dimethyl malonate from 1,3-propanediol, right? The starting compound being used in the article I wrote about in my previous post...

Greetz A


Nicodem

  • Guest
4-methyl-hydroxybutanoate?
« Reply #13 on: August 07, 2004, 05:14:00 AM »
What do you mean by:
...the product from oxidizing 1,4-butanediol, 4-methyl-hydroxybutanoate, looks more like it could result in valerolactone...

You can't get any 4-methyl-hydroxybutanoate by the oxidation of 1,4-butanediol. You can only get methyl 4-hydroxy-butanoate by the reaction as you propose it. Though in my opinion you would get mostly just GBL. The methyl ester just like the lactone should hydrolyze with the aid of sodium hydroxide in sodium GHB salt.


Rhodium

  • Guest
Maybe this diagram will help you understand...
« Reply #14 on: August 07, 2004, 07:50:00 AM »
Maybe this diagram will help you understand why there is a vast difference between the ester Methyl 4-Hydroxybutanoate (the product in the hypochlorite oxidation of butanediol in methanol) and the hydroxy-acid 4-Methyl-4-Hydroxybutanoate (the free acid corresponding to gamma-valerolactone).



gamma-Valerolactone and 4-Methyl-4-Hydroxybutanoate are active, see

https://www.thevespiary.org/rhodium/Rhodium/chemistry/4-methyl-ghb.html




armageddon

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sorry for my typo - meant ...
« Reply #15 on: August 07, 2004, 08:05:00 PM »
sorry for my typo - meant methyl-4-hydroxybutanoate, not 4-methyl-4-OH-...

So 4-hydroxy-butanoic acid methyl ester hydrolyzes to 4-hydroxybutyric acid when treated with hot aequ. NaOH?

And upon treatment of 1,4-BDO with CaOCl/CH3OH, one would get a mixture of 4-hydroxybutanoic acid methyl ester and gamma-butyrolactone? Which is completely turned to GHB by the usual lye procedure?

Did I get that right so far?

Greetz A


Rhodium

  • Guest
Yes, everything you just said is correct.
« Reply #16 on: August 08, 2004, 05:52:00 AM »
Yes, everything you just said is correct. Just keep in mind that the basic hydrolysis goes like this:

4-hydroxy-butanoic acid methyl ester + NaOH -> Sodium 4-hydroxybutyrate + Methanol

You should remove that methanol before ingesting any of the resulting NaGHB.


armageddon

  • Guest
maybe I should've UTFSE.. *lol*
« Reply #17 on: August 08, 2004, 01:32:00 PM »
Good old FSE revealed the following:

Post 436497

(Rhodium: "NMP/GBL/dimethylmaleate separation", Chemicals & Equipment)


Same principle behind it, isn't it? The ester gets hydrolyzed and only the "GBL"-remainder of its molecule rearranges upon acidification, while CH3OH is formed?  :)

Greetz, A


Rhodium

  • Guest
Yes, that's one way of expressing it...
« Reply #18 on: August 08, 2004, 06:53:00 PM »
Yes, that's one way of expressing it - with the difference being that there is only one ester present in this case.


Rhodium

  • Guest
Oxidative Esterification of Butanediol to GBL
« Reply #19 on: September 21, 2004, 11:51:00 AM »
Oxidative Esterification of Primary Alcohols by NaBrO3/NaHSO3 Reagent in Aqueous Medium
Kiyoshi Takase, Haruyoshi Masada, Osamu Kai, Yutaka Nishiyama, Satoshi Sakaguchi, and Yasutaka Ishii

Chemistry Letters 871-872 (1995)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.nabro3-nahso3.pdf)

Abstract
NaBrO3 combined with NaHSO3 was found to be an efficient reagent for the oxidative esterification of primary alcohols. Thus, a variety of esters was prepared from primary alcohols, aldehydes, and acetals in aqueous medium under mild conditions. Treatment of ?,?-diols with NaBrO3/NaHSO3 reagent afforded the corresponding lactones and/or dicarboxylic acids in fair yields.
____ ___ __ _

Selective, Heterogeneous Oxidation of Alcohols and Diols with Potassium Permanganate
Charles W. Jefford and Ying Wang

J. Chem. Soc. Chem. Commun., 634-635 (1988)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.kmno4-cuso4.pdf)

Abstract
Primary alcohols can be conveniently oxidized to carboxylic acids using solid KMnO4/CuSO4·5H2O/KOH in an organic solvent; 1,4- and 1,5-diols can be selectively oxidized to the corresponding lactones using appropriate mixtures of KMnO4/CuSO4·5H2O without added base.
____ ___ __ _

Oxidation of Alcohols with Peracetic Acid in Ethyl Acetate in the Presence of Sodium Bromide
Takashi Morimoto, Masao Hirano, Takayoshi Hamaguchi, Masahide Shimoyama, and Xiumin Zhuang

Bull. Chem. Soc. Jpn., 65, 703-706 (1992)

(https://www.thevespiary.org/rhodium/Rhodium/pdf/bd2gbl.peracetic-nabr.pdf)

Abstract
Aliphatic primary alcohols and 1,?-diols were oxidized to the dimeric esters and lactones, respectively, by peracetic acid in ethyl acetate in the presence of sodium bromide under mild conditions. Aliphatic secondary and benzylic alcohols were converted smoothly to the corresponding carbonyl compounds by the same system.