JP2003522742A - Method for producing substituted formamide - Google Patents

Abstract

  (57) [Summary] Oxidation of the amine in the presence of a catalyst produces a substituted formamide.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to a method of oxidizing a side chain of a tertiary amine in a gas phase in the presence of a catalyst to produce a substituted formamide.

BACKGROUND Catalytic oxidation of tertiary amines in the liquid phase to form substituted formamides has been disclosed in US Pat. No. 4,543,424 and references cited therein.

In US Pat. No. 3,483,210, the methyl group of a tertiary N-methylamine is selected from the platinum group transition metals using oxygen at atmospheric pressure and amine in the liquid phase. Oxidation to formyl groups in the presence of a homogeneous catalyst is disclosed.

Methylamine is produced by carrying out a gas phase reaction of methanol and ammonia with an acidic catalyst such as silica-alumina. A typical molar ratio of the amine produced when using this catalyst is CH ₃ NH ₂ : (CH ₃ ) ₂ NH:
(CH ₃ ) ₃ N = 17: 21: 62. However, dimethylamine has the highest demand on the market. One of the primary uses of this amine is in the production of solvents such as dimethylformamide. Many of the commercially desired productions of dimethylamine are typically carried out by reacting trimethylamine with additional methanol. There is a need to improve the efficiency of the procedure when trimethylamine is used in the preparation of additional dimethylamine or its derivatives, such as dimethylformamide.

[0005]     (Summary of Invention)   The present invention discloses a process for preparing a substituted formamide, which process comprises: (i) in a gas phase
Oxygen and formula CH₃NR₂[Wherein R is C₁To C₈Alkyl, phenyl, naphthyl
, And C₁To C_FourAlkyl-substituted phenyl or mixtures thereof
A compound represented by formula (a)_xAu_yM_{1- (x + y)}[formula
Where A is selected from the group consisting of Cu, Cr, Ru, Co and combinations thereof.
Selected, M is Al, Mg, Nb, Si, Ti, Zr and combinations thereof.
Is selected from the group consisting of: x is 0.001 to 0.5 and y is 0
To 0.2], or xerogels or aero
Gels, (b) H_FourPMo₁₁VO₄₀, H_FivePMo_TenV₂O₄₀,
H₆PMo₉V₃O₄₀And H₇P₂Mo₁₇VO₆₂A hetero selected from the group consisting of
Polyacids (heteropolyacids), (c) H_{4+ (6-z)}PMo_TenVEO_{Four 0} , H_{5+ (6-z)}PMo₉V₂EO₄₀, H_{6+ (6-z)}PMo₈V₃EO₄₀And H_{7+ (6-z)}P ₂ Mo₁₆VEO₆₂[Where E is from the group consisting of Cu, Cr, Zn and Co.
Is an element selected, and z is the valence of E]
Metal-substituted heteropolyacid, (d) Q_qH_FourPMo₁₁VO₄₀, Q_qH_FivePMo_TenV₂
O₄₀, Q_qH₆PMo₉V₃O₄₀, Q_qH₇P₂Mo₁₇VO₆₂, Q_qH_{4+ (6-z)}PMo_Ten
VEO₄₀, Q_qH_{5+ (6-z)}PMo₉V₂EO₄₀, Q_qH_{6+ (6-z)}PMo₈V₃EO₄₀And
And Q_qH_{7+ (6-z)}P₂Mo₁₆VEO₆₂[Where Q is a group consisting of Ag and Cs
, And q is 0 to the number of hydrogen atoms multiplied by 0.5 when Q is Ag.
Is a digit and q is 0 to the number of hydrogen atoms multiplied by 1 when Q is Cs.
A heteropolyacid salt selected from the group consisting of:_r(HPA
)_sM_{1- (r + s)}[Where r is 0.001 to 0.1 and s is 0.001
, 0.05 and HPA is based on the catalysts (b) and (c) heteropoly acid and heparin.
Selected from the group consisting of telopolyacid salts, and M is Al, Mg, Nb, Si,
Selected from the group consisting of Ti and Zr] or xerogel or aeroge
Le complex, and (f) formula (Bi_tCo_uNi_v)_wMo_1-wO_a[Wherein t, u and
And v are each independently 0 to 1, t + u + v = 1, and w is 0.0
1 to 0.75, and a is 1.125 to 4.875]
Contacting in the presence of a catalyst selected from the group consisting of metal oxides, and (i
i) Formula HC (O) NR₂Including recovering an N-substituted formamide represented by
Become.

Also, the formula A _x Au _y M _{1- (x + y)} [wherein A is selected from the group consisting of Cu, Cr, Ru, Co and combinations thereof, and M is Al, Mg, Nb, Si, T
selected from the group consisting of i, Zr and combinations thereof, and x is 0.001
To 0.5, and y is 0 to 0.2]. Also disclosed are compositions comprising a xerogel or aerogel.

Further, the formula Ru _r (HPA) _s M _{1- (r + s)} [where r is 0.001 to 0.1, s is 0.001 to 0.05, and HPA is selected from the group consisting of heteropolyacids and heteropolyacid salts, and M is Al, Mg, Nb, Si,
Selected from the group consisting of Ti, Zr]. Also disclosed is a composition comprising a xerogel or an aerogel composite.

(Detailed Description) The tertiary amine, which is the starting material to be oxidized, has the formula CH ₃ NR ₂ [wherein R is
Selected from the group consisting of C ₁ to C ₈ alkyl, phenyl, naphthyl, and phenyl substituted with C ₁ to C ₄ alkyl, or mixtures thereof]. The oxidation product is any of the formamides corresponding to the formula HC (O) NR ₂ . Oxidation to produce dimethylformamide from trimethylamine is preferred.

The oxygen used in the method may be high purity oxygen, oxygen mixed with an inert gas, or air. The use of air is preferred.

The reaction is typically about 125 ° C. to about 450 ° C., preferably about 150 ° C. to about 2
Carried out at a temperature of 75 ° C. The pressure of this reaction is typically about 1 atmosphere (100 kPa)
To about 10 atmospheres (1000 kPa).

The oxidation product is recovered from the product mixture by conventional techniques such as fractional distillation.

The preparation of the catalysts described in this invention is carried out by various methods known in the art, such as impregnation, xerogel or aerogel formation, reflux and ion exchange to produce polyoxometallates, freeze-drying, spray-drying and spray-rose. It can be implemented by spray roasting or the like. Catalyst powders, extrudates and pellets as well as monoliths
oliths) can also be used as supports, provided that they have sufficient porosity for use in the reaction vessel.

The xerogel or aerogel used in the present invention comprises a matrix material derived from a solution of one or more matrix components [matrix component (s)], and one active catalyst component is contained in the matrix material. Alternatively, two or more [which are derived from one or more dissolved components, one or two or more] are incorporated. The matrix consists of oxides and oxyhydroxides derived from the hydrolysis of alkoxides and condensation with other reagents.
It is a skeletal framework of droxides). Such a framework typically comprises 30% or more by weight of the total catalyst composition. The matrix material comprises xerogels or aerogels or mixtures thereof, which are oxides / hydroxides of magnesium, silicon, titanium, zirconium or aluminum, in total 30 mol% to 99.9 mol% of the catalyst composition, It is preferably 65 to 85 mol%.

In the present invention, one or more metal alkoxides (eg, aluminum isopropoxide) can be used as a starting material in forming the gel.
The inorganic metal alkoxide used in the present invention may include any alkoxide having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms in the alkoxide group, which are preferably soluble in a liquid reaction medium. Is. C ₁ -C ₄ alkoxide,
For example, aluminum isopropoxide, titanium isopropoxide and zirconium isopropoxide are suitable.

Commercially available alkoxides can be used. However, it is also possible to generate the inorganic alkoxide by other routes. Some examples include reacting a zero-valent metal with an alcohol directly in the presence of a catalyst. A large amount of alkoxide can be produced by the reaction of a metal halide and an alcohol. It is also possible to synthesize an alkoxy derivative by reacting alkoxide and alcohol by a ligand exchange reaction. Further, an alkoxide derivative is also produced by directly reacting a metal dialkylamide with an alcohol. Additional examples are D.M. C. Bradley et al. "Metal Alkoxide
s ", Academic Press (1978).

The first step in synthesizing alcohol-containing gels, ie, alcogels, is to first produce a non-aqueous solution of alkoxide and other reagents and to separate it with a protic solvent such as water. Forming a solution of. When the solution of the alkoxide and the solution containing the protic solvent are mixed, the alkoxide is polymerized to form a gel.

The solution medium used in the process should generally be a solvent for the inorganic alkoxide (s) used, and for the additional metal reagents and cocatalysts added during the single step synthesis. If it is desired to produce a highly dispersed material, it is preferred that all of the components be soluble in these individual media (aqueous and non-aqueous). When a soluble reagent is used in this manner, the active metal and the promoter reagent (promot
The mixing and dispersion of er reagents can occur in the near-atomic state, and in fact, they reflect the dispersibility they exhibit in their individual solutions. The precursor gel produced by this method will contain highly dispersed active metal and cocatalyst. The high dispersion results in catalyst metal particle sizes in the nanometer range.

The catalytic metal component of the gel is dissolved in another protic solvent (eg, water) and a solution of one or more of the catalytic metal compound is added to one or two matrix components.
An embodiment of mixing with one or more non-aqueous solutions is shown. Such catalytic metal component is dissolved in the same non-aqueous solution as the one or more matrix components, and water replenishment (aq
An embodiment using a transparent supplement is also shown.

The concentration of solvent used is typically related to the content of alkoxide. Ethanol and total alkoxide can be used in a molar ratio of 26.5: 1, but the ethanol: total alkoxide molar ratio can be about 5: 1 to 53: 1, or higher. With a large excess of alcohol, gelation generally does not occur immediately and some solvent may need to be evaporated. Lower concentrations of solvent will produce heavier gels with smaller pore volume and surface area.

In the present invention, water and any aqueous solution are added dropwise to alcohol-soluble alkoxide and other reagents for the purpose of inducing hydrolysis and condensation. Depending on such alkoxide system, a sensible gel point can be reached within minutes or hours. Total water to be added (including water existing in the aqueous solution) and Al, Mg, N to be added
The overall molar ratio of b, Si, Ti and Zr varies depending on the specific inorganic alkoxide to be reacted.

The water to alkoxide molar ratio used is generally about 0.1: 1 to 10: 1. However, in the case of zirconium (alkoxide) ₄ and titanium (alkoxide) ₄ , a ratio close to 4: 1 can be used, in the case of Mg (alkoxide) ₂ 2: 1 and in the case of Al (alkoxide) ₃ Is 3: 1, Nb (
Alkoxide) ₅ : 5: 1, Si (alkoxide) 4: 1:
Ratios close to 1 can be used. The amount of water used in this reaction is the amount calculated to hydrolyze the inorganic alkoxide in the reaction mixture. Lowering the ratio required for the hydrolysis of the alkoxide species results in partially hydrolyzed material, often reaching the gel point at a much slower rate, which is due to aging procedures and atmospheric Will depend on the presence of moisture.

Addition of an acidic or basic reagent to the inorganic alkoxide medium can influence the rate of hydrolysis and condensation reactions and is an oxide / hydroxide matrix derived from alkoxide precursors [in which Capture or incorporate the soluble metal and the cocatalyst reagent].
Generally, a pH in the range 1 to 12 can be used, with a pH in the range 1 to 6 being preferred.

After the reaction to form the alcogel of the present invention, it may be necessary to carry out some aging of the gel in order to complete the gelling process. The time of such aging can range from 1 minute to several days. All alcogels are generally aged for at least several hours in air at room temperature.

Removal of the solvent from the alcogel can be accomplished in several ways. Removal using vacuum drying or heating in air results in the formation of a xerogel.
An airgel of the material can typically be produced by charging it in a pressure device such as an autoclave. The solvent-containing gel produced by the present invention can be placed in an autoclave to contact it with a fluid at temperatures and pressures above and below the critical temperature and pressure of this fluid [supercritical fluid in the gel material By flowing until the solvent is no longer extracted by the supercritical fluid]. A variety of fluids can be used under these critical temperatures and pressures when performing such extraction to produce an airgel material. Examples of such fluids suitable for use in the present method include, but are not limited to, fluorochlorocarbons [a representative of which is Freon ™ fluorochloromethane (eg Freon ™).
(Trademark) 11 (CCl ₃ F), Freon (trademark) 12 (CCl ₂ F ₂ ) or F
reon ™ 114 (CClF ₂ CClF ₂ )), ammonia and carbon dioxide. Such extraction fluids are typically gaseous under atmospheric conditions, thus avoiding pore collapse caused by capillary forces occurring at the liquid / solid interface during drying. In most cases, the resulting material will have a greater surface area than that of the non-supercritically dried material.

The xerogels and aerogels thus produced can be described as precursor salts dispersed in an oxide or oxyhydroxide matrix. The theoretical maximum of hydroxyl content corresponds to the valence of the central metal atom. The final xerogel stoichiometry is also affected by the H ₂ O: alkoxide molar ratio, so that residual -OR groups will be present in the unaged gel. However, as polymerization and dehydration continue, they will convert to the corresponding -OH and -O groups when they react with atmospheric moisture. If crosslinking and polymerization continue, H ₂ O
Removal of -OH results in the condensation of -OH, i.e. a gel, which is also subject to aging (even if aging is carried out under inert conditions). To some extent, the extent of -OH crosslinking and conversion is shown by varying stoichiometry with respect to the hydroxyl content of the formula. For example, in the case of AlO _1.5-z (OH) _2z , z
, Which can range from 1.5 (totally hydroxyl) to 0 (totally oxide).

In another aspect of the invention, one or more inorganic metal colloids can be used as a starting material in forming the gel. Such colloids include colloidal alumina sol, colloidal zirconia sol, colloidal titania sol, colloidal mixed oxide sol, colloidal silica sol, and ternary system (ternar).
y) or higher order oxide sols and mixtures thereof. Some of such colloidal sols are commercially available. In addition, the method of generating colloid is also “Inorganic Colloid
Chemistry ", 1, 2 and 3, J. Chem. Wiley and Sons
, Inc. , 1935, there are several. The formation of colloids involves either nucleation and growth or subdivision or dispersion methods. For example, a hydrous titanium dioxide sol can be prepared by adding ammonium hydroxide to a solution of a tetravalent titanium salt and then deflocculating (redispersing) it with a dilute alkali. The zirconium oxide sol can be prepared by dialysis with sodium oxychloride. The preparation of other sols is described in that document.

[0027]   Commercial alkoxides such as tetraethyl orthosilicate and organotitanium
Acid ester [trademark "Tyzor" by DuPont Company ^R "Sold under" and the like. Also, using various routes
It is also possible to prepare inorganic alkoxides. Examples include zero-valent metals
And the reaction of alcohols with alcohols in the presence of a suitable catalyst, and metal halogens.
And a method of reacting an alcohol with an alcohol. Alkoxide and alcohol
It is also possible to synthesize the alkoxy derivative by reacting with a ligand exchange reaction.
It is also possible to directly react a metal dialkylamide with an alcohol to obtain an alcohol.
A side derivative is produced. Additional examples are D.M. C. Bradley et al., "Metal
  Alkoxides "(Academic Press, 1978).
Has been.

In a preferred embodiment of the method of the present invention, a colloidal sol, aquasol, previously formed in water is used. The colloidal particles contained in this aquasol range in size from 2 to 50 nanometers. Generally, the primary particle size (p
The smaller the primary particle sizes, the smaller (2 to 5).
nm) is more suitable. The pre-formed colloid contains 10 to 35% by weight of colloidal oxide or other material, depending on the stabilization method.
A final de-stabilized colloid (final de-stabi) after addition of a metal component exhibiting activity (either as a catalyst for partial oxidation reaction or as a promoter).
The amount of solids contained in the sized colloids may generally be about 1 to 35% by weight, preferably about 1 to 20% by weight.

During the addition of the soluble salt of the cationic species of the main catalyst and cocatalyst, the acid or base (
Destabilize the colloidal oxides or mixtures thereof by adding either (altering the pH) or removing the solvent. Polymerization and cross-linking reactions can occur between surface functional groups, such as surface hydroxyls, when the particles are close enough to contact when destabilizing. In one aspect of the invention, the colloid, which is an originally stable, heterogeneous dispersion of oxides and other species in a solvent, is destabilized to form a colloidal gel. Destabilization may include addition of soluble salts such as chlorides or nitrates in some cases (pH of colloidal suspension upon addition of acid or base).
And ionic strength changes) or by removal of solvent. p
H generally changes with the addition of soluble salts. This is generally preferred over solvent removal. Generally, pH's in the range of about 0 to about 12 can be used for destabilizing the colloids, however, very high pH's can cause aggregation and precipitation. For this reason, a pH in the range of about 2 to 8 is generally preferred.

The medium used in the method is typically an aqueous medium, but it is also possible to use non-aqueous colloids. The additional metal or inorganic reagent used (ie salt of Cr or cocatalyst) should be soluble in suitable aqueous and non-aqueous media.

When the solvent is removed from the gel to produce either an aerogel or a xerogel, it can be accomplished using several methods described above.

The preparation of the heteropolyacid (HPA) catalysts [catalysts (b), (c) and (d)] of the present invention is typically an aqueous method.
process). An appropriate amount of the appropriate reagent is placed in water and heated to an elevated temperature [said amount is the desired heterotransition metal in which vanadium is used as a co-catalyst to replace the transition metal.
substituted vanadium promoted hetero
polyacid)] is calculated. Normal temperature is reflux (
(100 ° C.) temperature and normal time is overnight. However, time and temperature are not critical as long as the time / temperature is sufficient to allow all of the reagents to go into solution to form a clear, usually highly colored solution. In some cases, the reaction is completed under reflux within 2 hours, in other cases longer.

The reaction is preferably carried out in an air atmosphere. It is also possible to use an inert atmosphere. The method is generally carried out under normal atmospheric pressure, but it is also possible to use elevated or reduced pressure. Although stirring is not necessary, it is usually performed for the purpose of promoting heat transfer.

Commercial reagents are used in the preparation of this HPA. The purity of such reagents needs to be known so that the total amount required can be calculated. The amount of reagent used should be within ± 5% of the stoichiometric amount, preferably within ± 2%.

The product is isolated by evaporating the reaction mixture to dryness. This may be done by any known method and typically a vacuum is used to speed up the process. This isolated product can be used as is, or if the specific equipment is used for the next HPA use, the product HPA can be processed into particles of various sizes and shapes before use. Alternatively, it can be processed. That is, this product is crushed or pelletized depending on the requirements for use in a particular device,
It can be in briquette tabular form, or in other forms.

A variation on the above-described preliminary procedure involves the thermal removal of ammonia after the ammonium salt of the desired HPA has been prepared. The second alternative is to generate the desired acid form of HPA by ion exchange.

The present invention also includes a heteropolyacid and a suitable sol gel derivative.
It is also possible to use xerosol or airgel composites of erive material), which are described as catalyst (e) in the summary part of the invention. The synthesis of such a complex is carried out by adding a water-soluble heteropolyacid to an alkoxide solution while hydrolyzing the alkoxide or by destabilizing the aquasol to the aquasol to form a gel material. It can be carried out by adding before or during. It is also possible to add other inorganic reagents during such additions (eg Ru as the cationic species that can serve as the counterion of the heteropolyacid).

For some catalyst compositions [eg, compositions described as catalyst (f) in the Summary of the Invention], a lyophilization procedure can be used if the catalyst precursor is soluble in water or another solvent. And it is useful when it can be frozen quickly (within 1 minute). The precursor salt is dissolved in a solution or solvent in an appropriate amount to produce a fine colloid. The solution is then rapidly cooled and frozen by immersion in a suitable medium such as liquid nitrogen. If the solution is frozen rapidly, the salt and the other components will remain intimately mixed and will never separate to any significant degree. The frozen solid is transferred to the freeze drying room. Water vapor is removed by vacuum evacuation while maintaining the solution in a frozen state.

The spray-drying procedure is described in the summary section of the present invention given above for catalysts (a), (b).
, (C), (d), (e) and (f), involving the use of solutions, colloids or slurries containing catalyst precursors or catalyst components. This technique consists of atomizing such a liquid (usually but not exclusively an aqueous solution) into a spray and evaporating the water as a result of contacting the spray with a drying medium (usually hot air). Drying of the spray is allowed to proceed until the desired moisture content in the resulting dry particles and the product is recovered by a suitable separation technique (usually cyclone separation). For a detailed explanation of the spray drying method, see K Masters,
Spray Drying Handbook, 4th Edition (Longman Sc)
Authentic and Technical, John Wiley an
d Sons, NY) c. 1985.

Spray roasting also involves the use of solutions or colloids, but in general
It involves drying and calcination (at higher temperatures) in one process step to produce a catalyst powder.

EXAMPLES In the experiments described in the present invention, two section Vs were used.
An irtis lyophilizer was used. Refrigerated shelves were used to prevent the frozen solids from thawing during evacuation. All percentages in the examples below are by weight unless otherwise stated. General Procedure for Catalytic Testing In a typical test, a 1/4 "(6.4 mm) stainless steel reactor was charged with a constant volume (0.625 mL) of catalyst (silica wool was used to hold it in place). And heated to the initial reaction temperature (175 ° C.) under nitrogen, the gas feeder was a constant mixture of 1.5% trimethylamine / 20% oxygen / 78.5% nitrogen at 20.9 cc / min under 1 atm. The structure is such that it is conveyed to the reaction tank at a flow rate.Before taking a sample of the reaction tank, a sample of unreacted feed gas was sampled to measure the gas composition. The Hewlett-P equipped with two types of detectors (a flame ionization detector and a thermal conductivity detector).
The effluent gas was analyzed using an ackard Model 5890 gas chromatograph. The column used was (1) 60/80 mesh (0.25 / 0.18 mm)
10 '(3.05m) x1 / 8 "(3 with 3X molecular sieve
． 2 mm) stainless steel column (used to separate H ₂ O, N ₂ and CO) and 80 /
2 '(0 containing 100 mesh (0.18 / 0.15 mm) Haysep R ™ (copolymer of divinylbenzene and N-vinyl-2-pyrrolidone)
． 61m) combination of x1 / 8 "stainless steel column (3.2 mm) (used to separate between H ₂ O and CO ₂ and butane), and (2) 20mx0.53mm the DB
It included a 1 (dimethylpolysiloxane) capillary column (used to separate organics). Helium was used as the carrier gas in all columns. The analyzes for both column systems were performed simultaneously with samples taken separately from the two loops for the 500 microliter sample. A valve switching scheme was used to ensure that each sample was analyzed properly. The GC was programmed to control the temperature of the column in such a way that the entire analysis could be completed in 15.45 minutes.

The response factor of specific compounds was measured using the following two methods: (1)
Inject gas or liquid with a syringe, or (2) inject gas sample loop (
sample loop injections of cases).

After performing the analysis of the feed gas, a sample of the reaction gas was taken at each of three or four temperatures (175 ° C., 225 ° C., 275 ° C. and again 175 ° C.) and the same analysis as above was performed. went. The test was terminated by taking a final feed gas sample for analysis. Next, the data is collected and calculated, and the conversion rate of trimethylamine is%
And the selectivity to dimethylformamide and monomethylformamide was determined.

The results of the catalyst test are shown in Tables 1 to 5. Glossary T is temperature. CT is the contact time. TMA is (CH ₃ ) ₃ N. DMF is (CH ₃ ) ₂ NCHO. MMF is CH ₃ NHCHO.

Example 1 In a 150 mL Petri dish, 0.02 M AuCl ₃ solution in ethanol (21.
A solution of 0.349 M magnesium methoxide in ethanol (47.33 mL) was added with 776 mL) with gentle swirling. In the second stage, chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ aqueous solution [0.871
mL (0.5 M)] was added slowly. After confirming the gel point, the material was aged for at least 24 hours prior to use. The material was dried under vacuum at 120 ° C for 5 hours and then calcined in air at 250 ° C for 1 hour. 20 of this fired powder
Pellet at 000 psig (138 mPa), then -4 before use
Granulated with a 0, +60 mesh (-0.42, +0.25 mm) screen. The nominal metal composition of this catalyst was Au _0.025 Cr _0.025 Mg _0.95 .

Example 2 The following amounts of reagents were used: 0.05M aluminum isopropoxide solution in ethanol (68.19 mL), 0.02M AuCl ₃ solution in ethanol (1.74).
0 mL) and chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ aqueous solution [0.07 mL (0.5 M)], but following the same procedure as described in Example 1. The nominal metal composition of this catalyst was Au _0.01 Cr _0.01 Al _0.98 .

Example 3 Reagents in the following amounts: 0.6% by volume tetraethyl orthosilicate solution in ethanol (0.317 mL), 0.02 M AuCl ₃ solution in ethanol (22.436).
mL), 0.349M magnesium methoxide solution in ethanol (46.3M).
49 mL) and chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ aqueous solution [0.897 mL (0.5 M)], but following the same procedure as described in Example 1. The nominal metal composition of this catalyst was Au _0.025 Mg _0.9025 Cr _0.015 Si _0.0475 .

Example 4 The following amounts of reagents were used: a 0.5 M solution of aluminum isopropoxide in ethanol (69.821 mL) and chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃
The same procedure as described in Example 1 was followed except that it was used in an aqueous solution of CO ₂ ) ₇ [0.179 mL (0.5 M)]. The nominal metal composition of this catalyst was Cr _0.025 Al _{0.9 75} .

Example 5 The same general procedure as described in Example 1 was followed except that the reagents and stoichiometry were adjusted. After AuCl ₃ (0.9579 g) was dissolved in ethanol (50 mL), it was added to aluminum isopropoxide (24.51 g) dissolved in isopropanol (2500 mL). This was dissolved in a dry box in an inert atmosphere. Chromium hydroxide acetate (0.6351g) was added to water (1
ml) and then this solution was diluted with ethanol (10 mL) to prepare an aqueous solution of chromium. Nominal metal composition of this catalyst was Au _0.025 Al _{0.9 5} Cr _0.025.

Example 6 Reagents in the following amounts: 0.05M aluminum isopropoxide solution in ethanol (64.842 mL), 0.02M AuCl ₃ solution in ethanol (4.4).
9 mL), a solution of 0.349 M magnesium methoxide in ethanol (0.4
88 mL) and chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ aqueous solution [0.180 mL (0.5 M)], but following the same procedure as described in Example 1. The nominal metal composition of this catalyst was Au _0.075 Cr _0.025 Al _0.9025 Mg _0.0475 .

[0051]                                  Example 7   Reagents in the following amounts: 0.05M aluminum isopropoxide in ethanol
Solution (64.842 mL), 0.02 M AuCl in ethanol₃Solution (4.5
18 mL), a tetraethyl orthosilicate solution of 0.6% by volume in ethanol (
0.064 mL) and chromium hydroxide acetate (Cr₃(OH)₂(CH₃CO₂) ₇ The procedure described in Example 1 except that it was used in an aqueous solution [0.181 mL (0.5 M)].
Followed the same procedure in order. The nominal metal composition of this catalyst is Au._0.025Cr_0.025Al _0.9025 Si_0.0475Met.

Example 8 Reagents in the following amounts: 0.05M aluminum isopropoxide solution in ethanol (51.21 mL), 0.02M AuCl ₃ solution in ethanol (10.1).
07 mL), a tetraethyl orthosilicate solution of 0.6% by volume in ethanol (
0.952 mL), a 0.349 M solution of magnesium methoxide in ethanol (7.326 mL) and an aqueous solution of chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ [0.404 mL (0.5M )] Was used, but the same procedure as described in Example 1 was followed, with a nominal metal composition of Au _0.025 Cr _0.025 M.
It was g _0.32 Al _0.32 Si _0.32 .

Example 9 The following amounts of reagents were used: 0.02M AuCl ₃ solution in ethanol (49.396 m).
L), a 0.6% by volume solution of tetraethyl orthosilicate in ethanol (13.
25 mL), a solution of 0.349 M magnesium methoxide in ethanol (5.
371 mL) and chromium hydroxide acetate (Cr ₃ (OH) ₂ (CH ₃ CO ₂ ) ₇ aqueous solution [1.976 mL (0.5 M)], but following the same procedure as described in Example 1. The nominal metal composition of this catalyst was Au _0.025 Cr _0.025 Si _{0.90 25} Mg _0.0475 .

Example 10 Water (1000 mL), MoO ₃ (122.4 g) and vanadium pentoxide (4.6 g) were added to a 3 liter round bottom flask equipped with a dropping funnel, mechanical stirrer and reflux condenser. It was The slurry was brought to reflux. Next, phosphoric acid (1
1.5 g) aqueous solution was added slowly over 20 minutes until the desired stoichiometry was achieved. An orange-red solution formed after about 3 hours. Reflux was typically continued for 16 hours (overnight). The sample was dried in nitrogen at 120 ° C. for about 12 hours. The composition of this catalyst was H ₇ P ₂ Mo ₁₇ VO ₆₂ .

Example 11 The same procedure as described in Example 10 was used. Water (1000 mL) in a 3 liter round bottom flask equipped with a dropping funnel, mechanical stirrer and reflux condenser,
MoO ₃ (100.2 g), vanadium pentoxide (6.33 g) and CuO (5
． 5 g) was added. The slurry was brought to reflux. Next, phosphoric acid (8.1 g
) The aqueous solution was added slowly over 20 minutes until the desired stoichiometry was achieved. About 3
An orange-red solution formed after hours. Reflux typically 16 hours (overnight)
Continued. The sample was dried in nitrogen at 120 ° C. for about 12 hours. The composition of this catalyst was H _p PMo ₁₀ CuVO ₄₀ [where p is 8 and 9].

Example 12 Using the same procedure as described in Example 11, the following reagents were used: Water (10
00 mL), MoO ₃ (100.2 g), vanadium pentoxide (6.3 g), Cu
O (1.1g), Cr (NO 3) 3 · 9H 2 O (27.8g) and phosphoric acid (8.0
g) Aqueous solution. The composition of this catalyst is Cu _0.2 H _n PMo ₁₀ VCrO ₄₀ (where n is 3
． 6 and 3.8).

Example 13 Using the same procedure described in Example 11, the following reagents were used: Water (10
00 mL), MoO ₃ (100.2 g), vanadium pentoxide (6.3 g), Zn
Cl ₂ (9.5 g) and phosphoric acid (8.01 g) in water. The composition of this catalyst is H ₈ PM
It was o ₁₀ VZnO ₄₀ .

Example 14 H ₄ PMo ₁₁ using the procedure described in US Pat. No. 4,192,951.
VO ₄₀ was produced. Dibasic sodium phosphate in refluxing _{H 2 O (100mL) (Na} 2 HPO 4 · 7H 2 O, 48.75g) was dissolved. Sodium metavanadate (NaVO _3, 22.17g) was prepared second solution containing in H ₂ O (150mL). Sodium molybdate (Na ₂ MoO ₄ · 2H ₂ O, 411
． A third solution of 98 g) in H ₂ O (500 mL) was prepared. The three solutions were then combined with sulfuric acid H ₂ SO ₄ (205.4 mL). The combined solution was then placed in a 250 mL separatory funnel. Suitable heteropolyethers are obtained by adding diethyl ether.
te) was produced, taken out and dried to produce a free acid, thereby separating the heteropolyacid. This heteropolyacid was dissolved in water. The addition of silver carbonate produced a heteropolyacid with the proper stoichiometry. This material was evaporated to dryness before use. The composition of this catalyst was H ₂ Ag ₂ PMo ₁₁ VO ₄₀ .

Example 15 The same procedure as described in Example 10 was used. A 5 liter 3-neck round bottom flask (with heating mantle attached for reflux) was charged with molybdenum oxide (MoO ₃
, 440.9 g), vanadium oxide (V ₂ O ₅ , 25.3 g) and water (4000
mL) was added. After bringing to reflux, 85 wt% phosphoric acid (32.0 g) was added. After refluxing for about 16 hours, a red-brown solution had formed. Evaporation of this material to dryness produced the free acid. This heteropoly acid was dissolved in water. Addition of silver carbonate produced a heteropolyacid with the proper stoichiometry. This material was evaporated to dryness before use. The composition of this catalyst was H ₃ AgPMo ₁₁ VO ₄₀ .

[0060]                                 Example 16   The same procedure as described in Example 10 was used with the following reagents: water (10
00mL), MoO₃(9.0 g), vanadium pentoxide (1.27 g), CuO
(0.55 g) and phosphoric acid (1.6 g) in water. The composition of this catalyst is H_mPMo₉V ₂ CuO₄₀(Where m is 9, 10).

Example 17 Using the same procedure as described in Example 10, the following reagents were used: Water (10
00 mL), MoO ₃ (100.2 g), vanadium pentoxide (6.33 g), 2
, 4-Pentanedioate cobalt (17.9 g) and phosphoric acid (8.01 g) in water.
The composition of this catalyst was H ₈ PMo ₁₀ VCoO ₄₀ .

Example 18 A heteropoly acid "H ₄ PMo ₁₁ VO ₄₀ " was prepared in the following manner. 5
A 3-liter round-necked round-bottomed flask (with a heating mantle attached for the purpose of refluxing) molybdenum oxide (MoO ₃ , 440.9 g), vanadium oxide (V ₂ O ₅ , 25.
3 g) and water (4000 mL) were added. 85% by weight after taking to reflux
Phosphoric acid (32.0 g) was added. After refluxing for about 16 hours, a red-brown solution had formed. Evaporation of this material to dryness produced the free acid. Part of this material (4.4
53 g) was dissolved in water. Cs ₂ CO ₃ (1.63 g) was added to generate the final stoichiometry. The material was dried. The composition of this catalyst was Cs ₄ PMo ₁₁ VO ₄ .

Example 19 An airgel composite of “H ₄ PMo ₁₁ VO ₄₀ ”, which is a heteropolyacid, was prepared. Titanium n-butoxide (183.794 g) together with ethanol (206.45 mL) in a 1.5 liter resin container in an inert atmosphere dry box.
Was added. Ruthenium trichloride (6.23 in water (38.91 mL) in a dropping funnel.
g), glacial acetic acid (4.634 mL), nitric acid (3.618 mL), ethanol (20
6.45 mL) and H ₄ PMo ₁₁ produced as described in Example 18.
A second solution was prepared by dissolving VO ₄₀ (53.437 g) in water and then adding this to the alkoxide solution. The alcohol: metal molar ratio in this case is 26.5: 1. During the addition, the 1.5 liter resin vessel was placed under a nitrogen purge and the solution was gently stirred. A gel material formed, which was aged at room temperature for 24 hours, which was 20,000 psig (138
mPa), and then pelletized at -40, +60 mesh (-
It was granulated with a screen of 0.42, +0.25 mm). The nominal composition of the catalyst was _{Ru 0.05 (H 4 PMo 11 VO} 40) 0.05 (TiO 2) 0.9.

Example 20 The same procedure as described in Example 19 was followed except that the reagents and stoichiometry used were adjusted as indicated below. No heteropolyacid was added in this preparation.
Ethanol (412.5 mL) in a dry box in an inert atmosphere (under nitrogen)
Was used to dissolve zirconium isopropoxide (176.882 g). This was put in a 1.5-liter resin container. In the second dropping funnel, ethanol (
412.5 mL) containing solution to another aqueous solution [HNO ₃ (3.619 mL) and acetic acid (
RuCl ₃ (6.22) in H ₂ O (38.913 mL) containing 4.635 mL).
3 g) and H ₄ PMo ₁₁ VO ₄₀ (53.438 g) were prepared by dissolution]
Was used in combination with the zirconium isopropoxide solution in a dropwise manner. The ratio of H ₂ O: alkoxide was 4: 1. The resin container was covered with nitrogen during the dropping, and the solution was stirred during the dropping. The nominal composition of this catalyst is Ru _0.05 (H ₄ PMo ₁₁ VO ₄₀ ) _0.05 (Z
It was rO ₂ ) _0.9 .

Example 21 The same procedure as described in Example 20 was followed except that the reagents and stoichiometry used were adjusted as indicated below. Niobium ethoxide (143.195 g) was dissolved using ethanol (344 mL). HNO ₃ (3.77 mL) and acetic acid (
4.828 mL) and H ₂ O (40.534) containing ethanol (344 mL).
An aqueous solution was prepared by dissolving RuCl ₃ (5.186 g) and H ₄ PMo ₁₁ VO ₄₀ (44.532 g) in (mL). The water: alkoxide ratio was 5: 1. The nominal composition of this catalyst is Ru _0.05 (H ₄ PMo ₁₁ VO ₄₀ ) _0.05 (Nb
O _2.5 ) _0.9 .

[0066]   In Examples 22 to 28 and 30, l is ≧ 0 and 1.

Example 22 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Ti-n- in ethanol (371.21 mL)
Butoxad (163.373 g) was dissolved. An aqueous solution of chromium hydroxide acetate was prepared by dissolving chromium hydroxide acetate (24.1332 g) in H ₂ O (35.489 mL) and glacial acetic acid (8.24 mL). The ratio of H ₂ O: alkoxide was 4: 1. The nominal composition of this catalyst is Cr _0.2 (TiO _2-1 (O
H) ₂₁ ) _0.8 .

Example 23 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Tetraethyl orthosilicate (163.373 g) was dissolved in ethanol (371.21 mL). H ₂ O (34.589m
An aqueous solution of chromium hydroxide acetate was prepared by dissolving chromium hydroxide acetate (24.1332 g) in L). The ratio of H ₂ O: alkoxide is 4: 1.
Met. The nominal composition of this catalyst was Cr _0.2 (SiO _2-1 (OH) ₂₁ ) _0.8 .

Example 24 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Tetraethyl orthosilicate (74.9988 g) was dissolved in ethanol (278.4 mL). Chromium hydroxide acetate (
_{24.1332g), CoCl 2 (15.5807g)} , H 2 O (51.884m
L) and an aqueous solution of ethanol (278.41 mL) was used. H ₂ O:
The ratio of alkoxide was higher than 4: 1. Nominal composition of the catalyst was _{Cr 0. 2 Co 0.2 (SiO 2-1} (OH) 21) 0.6.

Example 25 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Tetraethyl orthosilicate (118.75 g) was dissolved in ethanol (435.84 mL). Ruthenium chloride (6.22
23 g), H ₂ O (41.07 mL) and ethanol (343.84 mL)
Aqueous solution consisting of HNO ₃ (3.82 mL) and glacial acetic acid (4.89 mL)
Was used. The ratio of H ₂ O: alkoxide was 4: 1. The nominal composition of this catalyst was Ru _0.05 (SiO _2-1 (OH) ₂₁ ) _0.95 .

Example 26 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Niobium ethoxide (151.11 g) was dissolved in ethanol (363.20 mL). An aqueous solution of ruthenium chloride (5.1858 g) in H ₂ O (42.786 mL) and ethanol (363.20 mL) was used, as well as HNO ₃ (3.979 mL) and glacial acetic acid (5.096 mL). The H ₂ O: alkoxide ratio was 5: 1. The nominal composition of the catalyst was _{Ru 0. 05 (NbO 2.5-1 (OH} ) 21) 0.95.

Example 27 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Titanium n- in ethanol (435.84 mL)
Butoxide (194.01 g) was dissolved. An aqueous solution of ruthenium chloride (6.2223 g) in H ₂ O (41.08 mL) and ethanol (45.843 mL) was used, as well as HNO ₃ (3.82 mL) and glacial acetic acid (4.89 mL). H ₂ O
The ratio of alkoxide was 4: 1. The nominal composition of this catalyst was Ru _0.05 (TiO _2-1 (OH) ₂₁ ) _0.95 .

Example 28 The same procedure as described in Example 20 was used except that the reagents and stoichiometry used were adjusted as indicated below. Zirconium n-propoxide [70 wt% in propanol (186.809 g)] was dissolved in ethanol (435.84 mL). An aqueous solution of ruthenium chloride (6.2229 g) in H ₂ O (41.075 mL) and ethanol (435.84 mL), and HNO ₃ (3.82 mL).
) And glacial acetic acid (4.89 mL) were used. The ratio of H ₂ O: alkoxide is 4: 1.
Met. The nominal composition of this catalyst was Ru _0.05 (ZrO _2-1 (OH) ₂₁ ) _0.95 .

Example 29 Acrylonitile catalyst (catalyst 41/49), commercially available from the Standard Oil Company (Ohio), was used.

[0075] Example 30 150 mL ammonium molybdate aqueous solution of 1.75M while gentle vortexing in Petri dishes _{((NH) 4) 6 Mo} 7 O 24 · 4H 2 O, 1.714
mL) of 0.5M bismuth nitrate solution [in nitric acid _{1M Bi (NO 3) 3 ·} 9H 2 O
(32.0 mL)], 1.0 M nickel chloride aqueous solution (
NiCl ₂ .6H ₂ O, 0.5 mL) and 1.0 M aqueous cobalt nitrate solution [Co
(NO ₃ ) ₂ · yH ₂ O, 0.5 mL]. The entire mixture was rapidly frozen in liquid nitrogen and then used in a two-section Virtis freeze dryer (Virtis).
It was evacuated and evaporated to dryness under vacuum for at least 24 hours using a Freezemobil and Unit dryer), but the dryer shelf was left frozen at about -10 ° C during the vacuum evacuation. The final dry material was calcined in air to 400 ° C. for 5 hours. This calcined powder is 20,000 psig (138 m
Pa) and then pelletized, and before use, -40, +60 mesh (-0
． 42, +0.25 mm) and granulated. The nominal composition of this catalyst was Mo _0.375 Bi _0.5 Ni _0.063 Co _0.063 O ₁ .

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) B01J 23/86 B01J 23/88 Z 23/88 27/199 Z 27/199 C07C 233/03 C07C 233/03 C07B 61/00 300 // C07B 61/00 300 B01J 23/64 102Z (72) Inventor Courtaquis, Costantinos Deino, New Jersey, USA 08085 Swearsboro Rough Aet Drive 241 F Term (Reference) 4G069 AA08 BA01C BA02C BA04C BA05C BA05C BA05C BA21C BA37 BA38 BB05A BB05B BB06A BB06B BB07A BB07B BC06A BC06B BC10A BC10B BC16A BC16B BC25A BC25B BC31A BC31B BC32A BC32B BC33A BC33B BC35A BC50A BC50B BC51A BC51B BC54A BC54B BC55A BC55B BC58A BC58B BC59A BC59B BC67A BC67B BC68B BC70A BC70B BD01A BD01B BD05A BD05B BD07A BD07B BE06C CB07 DA06 EA0 2Y FA01 FB09 FB30 FC02 FC08 4H006 AA02 AC53 AD10 BA02 BA05 BA07 BA09 BA10 BA12 BA13 BA14 BA20 BA23 BA30 BA33 BA35 BA74 BA75 BB61 BC10 BC11 BC13 BE30 4H039 CA71 CC60

Claims (12)

[Claims] 1. A method for producing a substituted formamide, which comprises (i) oxygen and CH ₃ NR _{2 in a} gas phase, wherein R is C ₁ to C ₈ alkyl, phenyl, naphthyl, and C ₁ To a compound selected from the group consisting of phenyl substituted with C ₄ alkyl or a mixture thereof]: (a) Formula A _x Au _y M _{1- (x + y)} [wherein A is Is selected from the group consisting of Cu, Cr, Ru, Co and combinations thereof, and M is Al, Mg, Nb, Si,
Selected from the group consisting of Ti, Zr and combinations thereof, and x is 0.00
1 to 0.5, and y is 0 to 0.2], (b) H ₄ PMo ₁₁ VO ₄₀ , H ₅ PMo ₁₀ V ₂ O ₄₀ , H ₆ PMo. Heteropolyacids selected from the group consisting of ₉ V ₃ O ₄₀ and H ₇ P ₂ Mo ₁₇ VO ₆₂ (c) H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , H _{5+ (6-z)} PMo ₉ V ₂ EO ₄₀ , H _{6+ (6-z )} PMo ₈ V ₃ EO ₄₀ and H _{7+ (6-z)} P ₂ Mo ₁₆ VEO ₆₂ [where E is Cu,
Cr, an element selected from the group consisting of Zn and Co, and z is a metal-substituted heteropolyacid is selected from the group consisting of a a] valence of _{E, (d) Q q H} 4 PMo 11 VO 40 , Q _q H ₅ PMo ₁₀ V ₂ O ₄₀ , Q _q H ₆ PMo ₉ V ₃
O ₄₀ , Q _q H ₇ P ₂ Mo ₁₇ VO ₆₂ , Q _q H _{4+ (6-z)} PMo ₁₀ VEO ₄₀ , Q _q H _{5+ (6-z)}
PMo ₉ V ₂ EO ₄₀ , Q _q H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and Q _q H _{7+ (6-z)} P ₂ Mo _{1 6} VEO ₆₂ [where Q is Ag and Selected from the group consisting of Cs and q
Is 0 to the number of hydrogen atoms multiplied by 0.5 when Q is Ag, and q
Is a heteropolyacid salt selected from the group consisting of 0 to the number of hydrogen atoms multiplied by 1 when Q is Cs, (e) the formula Ru _r (HPA) _s M _{1- (r + s )} [In the formula, r is from 0.001 to 0.1
, S is 0.001 to 0.05, and HPA is (b) and (c).
Is selected from the group consisting of heteropolyacids and heteropolyacid salts, and M is A
l, Mg, Nb, Si, xerogel or airgel composite represented by] is selected from the group consisting of Ti and Zr, and (f) formula _{(Bi t Co u Ni v)} w Mo 1-w O a [ Wherein t, u and v are each independently 0 to 1, t + u + v = 1, and w is 0.01 to 0.7.
5 and a is 1.125 to 4.875] in the presence of a catalyst selected from the group consisting of: a metal oxide represented by: and recovering the substituted formamide. A method comprising: 2. The method of claim 1, wherein the substituted formamide is an N-substituted formamide of the formula HC (O) NR ₂ . 3. The method of claim 1, wherein the oxygen is selected from the group consisting of substantially pure oxygen, air, and oxygen mixed with an inert gas. 4. The contact is performed at about 125 ° C. under a pressure of about 1 atm to about 10 atm.
The method of claim 1 performed at a temperature of from about 450 ° C. 5. The method of claim 4, wherein the temperature is about 150 ° C. to about 275 ° C. 6. The method according to claim 1, wherein the substituted formamide is recovered by fractional distillation. 7. The xerogel or aerogel of (a) or (e) is formed from a metal alkoxide selected from the group consisting of aluminum isopropoxide, titanium isopropoxide and zirconium isopropoxide. the method of. 8. The xerogel or aerogel of (a) or (e) is converted into an alumina sol, a colloidal zirconia sol, a colloidal titania sol, a colloidal mixed oxide sol, a colloidal silica sol, a ternary system or higher grade oxide. The method of claim 1 formed from an inorganic metal colloid selected from the group consisting of the sols and mixtures thereof. 9. The method of claim 8 wherein the xerogel or aerogel of claim 1 is formed from a preformed aquasol. 10. The formula A _x Au _y M _{1- (x + y)} [wherein A represents Cu, Cr, Ru,
Selected from the group consisting of Co and combinations thereof, M being Al, Mg, N
selected from the group consisting of b, Si, Ti, Zr, and combinations thereof, x is 0.001 to 0.5, and y is 0 to 0.2]. A composition comprising: 11. The formula Ru _r (HPA) _s M _{1- (r + s) wherein} r is 0.001
To 0.1, s is 0.001 to 0.05, HPA is selected from the group consisting of heteropolyacids and heteropolyacid salts, and M is Al, Mg,
Selected from the group consisting of Nb, Si, Ti, Zr], the composition comprising a xerogel or an airgel composite. 12. The heteropolyacid and heteropolyacid salt are H ₄ PMo ₁₁ V.
O ₄₀ , H ₅ PMo ₁₀ V ₂ O ₄₀ , H ₆ PMo ₉ V ₃ O ₄₀ , H ₇ P ₂ Mo ₁₇ VO ₆₂ , H _{4+ (6- z)} PMo ₁₀ VEO ₄₀ , H _{5+ (6-z )} PMo ₉ V ₂ EO ₄₀ , H _{6+ (6-z)} PMo ₈ V ₃ EO ₄₀ and H _{7+ (6-z)} P ₂ Mo ₁₆ VEO ₆₂ [where E is Cu, Cr, Zn and C
12. The composition of claim 11, wherein the element is selected from the group consisting of o and z is the valence of E].