JPS6034962A - 4,4-dihalohexahydrophthalic acid anhydride and 4-fluorotetrahydrophthalic acid anhydride, manufacture and use - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Cross-reference to Related Applications This application is filed in co-pending United States Patent Application Serial No. 1I9.3. g! This is a continuation-in-part application of No. rA.

BACKGROUND OF THE INVENTION The present invention relates to novel coufluoro l,co,left,6-titrahydrophthalic anhydrides of the formula: Methods of making and using these compounds are also disclosed.

The compounds of the present invention are useful as chemical intermediates for the synthesis of various end products. In particular, Gu.

Goo-dihalohexahydrontal anhydride and gou-fluorotetrahydrophthalic anhydride are useful in the synthesis of gou-fluorophthalic anhydride1, and terfluorophthalic anhydride is also used as an aromatic ether and thioether anhydride curing agent, oxidation inhibitor, useful in the production of polyetherimide polymers.

The utility of gou-fluorophthalic anhydride and various prior art methods for its synthesis are described in U.S. Pat. g! ;0,91.
! r and 3.9 &, 3:l/. An alternative method for synthesizing cufluoro-t77 talic anhydride directly from 4t,lI-dihalohexahydrophthalic anhydride by simultaneous dehydrohalogenation and dehydrogenation of the present invention is disclosed in the present application filed concurrently with the present application. David Y. Tongue, transferred to the same assignee as
, Tang) ``Process for the Prepara
tion of41- Fluoro phthali
c Anhydride)”.

The following US patents provide further background to the chemistry of cyclic anhydrides and halo-substituted cyclic anhydrides. Shak (S)
haw) et al., No. 9/, g-3; Clifford (C1i f ord) et al., fa 2.398-,
No. 26; Bar = - (Barney) No.: l,')
A'l,! ; No. 97; Mother Trick (Patrick)
et al., 3. :l'IO, ri9ko; acetiis (A
cetia) No. 3.3'lt,! ; Deku No.: Siegart et al., No. 3.4'gO, Otsu No. 67; Gormley et al., m, ?
, g/9.6! ig issue; griffith
) et al. q, oas, 11. og issue; Tsujimoto ('rs
Ujtmoto) et al., 3θ, No. 2,394.

The preparation of tetrahydrophthalic anhydride and its aromatization by dehydrogenation under limited circumstances is known in the chemical literature. Skvarchenko et al. (Ovshchey Kimmy) describe the aromatization of chloro-substituted tetrahydrophthalic anhydrides by heating with phosphorus pentoxide.

However, in the aromatization method described above, decalization also occurs along with the formation of the corresponding chloro-substituted benzene compound.

The preparation of tetrahydrophthalic acid and anhydrides and their aromatization are reviewed in Suf Gurnaen 3F/-Left g9 page.

Bergmann CJ, Amer, C
hem, 8oc,,AL/71A/91I2>':l
describe the aromatization of the tetrahydrophthalic anhydride product of the Diels-Alder reaction and state that dehydrogenation occurs when the tetrahydrophthalic anhydride product is boiled in nitrobenzene. However, it is also stated that no dehydrogenation occurs when using p-bromonitrobenzene or p-chloronitrobenzene or chem-') = ) lobenzene in xylene. Furthermore, it has been found that when the inventive nosohalohexahydrophthalic anhydride is dehydrogenated in nitrobenzene, a portion of the nitrobenzene is reduced to aniline.

Aniline reacts with anhydride groups on either the starting material or the product to form imides, thus reducing the yield of the desired product.

The preparation of the corresponding /-fluorocycloalkenes from /, /-difluorocycloalkanes by reaction with anhydrous alumina has been described by Strobach et al. [J
, Org, Chem, , Vol. 8. g/g-g;
10 (/?'#)] is described.

Goo Fluoro/, 2, 3. The preparation of is-tetrahydrontal acid anhydride is disclosed in US Pat. It is described in /, l, /2 issue. This reference states that this isomer is prepared by reaction of fluoroprene (:t-fluoro-/,3-f-tadiene) with maleic anhydride. This compound is reported to be hydrolyzed fluorophthalic acid.

The main object of the present invention is to provide new intermediate compounds useful in the synthesis of q-fluorophthalic anhydride.

Another object of the present invention is to provide a commercially attractive synthetic route for the production of terfluorophthalic anhydride.

SUMMARY OF THE INVENTION In accordance with the present invention, a novel glue, kudihalohexahydrophthalic anhydride, is prepared by reaction of guchlorotetrahydrophthalic anhydride with hydrogen fluoride. This reaction can be shown as below.

Here, Y is chlorine or fluorine.

This reaction actually produces a mixture of l-chloro-g-fluorohexahydrophthalic anhydride and caged fluorohexahydrophthalic anhydride. The relative proportions of each compound depend on the degree of fluorination of the substrate. Either or both of these compounds can be heated in the presence of an effective amount of basic alumina to produce an isomer mixture of g-fluorotetrahydrophthalic anhydride as described below.

0 0 0 , -4 △-3 Here, Y is fluorine or fluorine. In this reaction,
The Δ-3 isomer of g-fluorotetrahydrophthalic anhydride is a new compound.

Either or both of the lI-fluorotetrahydrontal acid anhydrides can then be aromatized by heating in the presence of a dehydrogenation catalyst to produce gfluorophthalic anhydride.

Suitable dehydrogenation catalysts include supported or unsupported yellow metals (e.g. platinum, radium, rhodium, ruthenium, iridium), nickel, l-alumina, chromium oxide, molybdenum oxide, tungsten oxide, Contains vanadium and rhenium. A preferred catalyst system is palladium on carbon. The basic aromatization reaction is shown below.

1 Description of the Preferred Embodiments The 1I, 11I-dihalohexahydrophthalic anhydride of the present invention is prepared by the reaction of hichlorotetrahydrophthalic anhydride and hydrogen fluoride as described below.

(1) The starting material for reaction (1), chlorotetrahydrophthalic anhydride, is a commercially available product and can be conveniently prepared by the reaction of chloroprene with maleic anhydride as described below.

Both starting materials for reaction (2) are readily available from commercial sources.

Reaction (1) is suitably carried out in a liquid phase at normal pressure or under applied or autogenous pressure between about Occ and about isθ°C.
preferably in the range of from about 20''C to about 7[theta]C. The rate of reaction is humidity dependent; the lower the temperature, the lower the rate of reaction.

The molar ratio of the reaction, HF:+-chlorodetrahydrophthalic anhydride, can vary considerably and typically ranges from about /, /: / to about 25:/. The reaction will occur at lower molar ratios, but the conversion rate will be lower. Higher molar ratios may also be used, but are generally not economical. When you want the highest yield of Dark Roro-Hirofluorohexahydrophthalic anhydride, approximately
It is preferred to use a ratio of HFi'-chlorotetrahydrophthalic anhydride in the range of F/ to about Coni/. ri,<
When the highest yield of 1-nofluorohexahydrophthalic anhydride is desired, it is preferred to use a ratio of about 2:/ to about 2.1/. If you want to maximize the yield of dark fluorohexahydrophthalic anhydride,
Preferably, the reaction is carried out in the absence of a catalyst. If you want to maximize the yield of caged fluorohexahydrophthalic anhydride and increase the conversion rate, at a temperature of 70 oc, 1/gO~'I-! ;l-light Kp/
It is preferable to carry out the reaction at an autogenous pressure of crIL21'-dipressure (Otsu θ-63 psig) at a molar ratio of HF:Hiro-chlorotetrahydrophthalic anhydride of g;/. The reaction rate can also be increased by the use of Lewis acid catalysts. Typical Lewis acid catalysts include, for example, aluminum chloride, antimony trichloride, antimony pentachloride, antimony trifluoride, antimony trifluoride, antimony oxychloride, molybdenum pentachloride, ferric chloride, ferrous chloride, etc. are included.

The crude reaction product of hydrogen fluoride and chlorotetrahydrophthalic anhydride according to the method of the present invention is
It contains a mixture of fluorohexahydrophthalic anhydride and 1LL-difluorohexahydrophthalic anhydride, the proportions of each depending on the reaction conditions indicated above. The anhydride product can be separated and isolated by conventional physical separation techniques such as fractional crystallization or vacuum distillation.

The +,+-nofluorohexahydrophthalic anhydride of the present invention is manufactured by David Y., Tang, filed concurrently with this application and assigned under the same permission as this application.
Tang)'s "Process for the Preparation of I-Fluorophthalic Anhydride"
ion ofll-Fluorophthallc A
can be used directly in the synthesis of fluorophthalic anhydride by the method more fully described in the US patent application entitled ``Nhydride''. fluorotetrahydrophthalic anhydride is used to prepare fluorotetrahydrophthalic anhydride, and then the fluorotetrahydrophthalic anhydride is used to synthesize 9-fluorophthalic anhydride as detailed herein. be able to.

The former method requires fewer processing steps than the latter method, but results in lower overall product yields. In any case, the crude reaction product of hydrogen fluoride and goochlorotetrahydrophthalic anhydride can be used in any of the above processes without the need for separation into the individual components. However, since Hiro-chloro-gu-fluorohexahydrophthalic anhydride may generate some group-chlorophthalic acid in the next reaction, the yield of Gu-chloro-gu-fluorohexahydrophthalic anhydride is It is preferable to utilize the above process conditions to achieve the best results.

+,+-Dihalohexahydrophthalic anhydride is hydrolyzed by conventional methods such as treatment with water to produce the corresponding acid,
That is, H-chloro-g-fluorohexahydrophthalic acid and Hq, a-nofluorohexahydrophthalic acid can be produced.

The +,+-dihalohexahydrophthalic anhydride produced by Book Q Mei 1/C is heated in the presence of basic alumina to obtain the isomerism of Hiroshi-fluorotetrahydrophthalic anhydride according to the following reaction. body mixtures can be produced.

0 0 0 (, jl where Y is chlorine or fluorine. In reaction (3), the Δ-6 isomer of gfluorotetrahydrophthalic anhydride is a new compound. According to the law, this compound is cufluoro/.

Ko,! It is called r,;-tetrahyrofucric anhydride.

Reaction (3) is usually carried out in a liquid phase, about /! ;O'C ~ approx.
The reaction is carried out at a temperature in the range of 270"C. A high boiling solvent such as sulfolane is commonly used. Alternatively, the reaction is carried out in the gas phase, suitably at a temperature of about 200C to about 300C. In either case, atmospheric or autogenous pressure conditions can be used.

The required amount of basic alumina generally ranges from about 7% to about 7.20% by weight of the reactants, preferably from about S to about 5% by weight of the reactants.
This is within the weight range. As known to those skilled in the art, basic alumina is a form of alumina that has lost a significant amount of hydrogen ions and can be conveniently prepared by reacting alumina with sodium hydroxide. The role of the basic alumina in the reaction is to dehydrohalogenate the +,+-dihalotetrahydrophthalic anhydride.

Separation of the isomers in the reaction products can only be achieved with great difficulty because of the similar chemical and physical properties of the isomers. However, separation is generally not necessary or desirable in many cases.

Hiro-fluorophthalic anhydride is obtained by heating Hiro-fluorotetrahydrophthalic anhydride in the presence of an effective amount of a suitable dehydrogenation catalyst.

This reaction can be shown as follows.

0 0 111 Either or both of the Hiro-fluorotetrahydrophthalic anhydride isomers can be used as a starting material with equal effectiveness. However, if the isomers are produced simultaneously, separation necessarily requires certain difficulties. Therefore,
Mixtures of isomers are generally preferred.

Reaction (4) can be carried out in the liquid phase or in the gas phase. Gas phase reactions are preferably carried out at temperatures in the range of about 200 to about 300°C and under normal or reduced pressure.

When reaction (4) is carried out in a liquid phase, /, 2. Solvents such as +-trichlorobenzene can be used.

If an insoluble catalyst is used, the catalyst is used in finely divided form;
Preferably, the catalyst is kept dispersed throughout the reaction medium by stirring.

This reaction preferably ranges from about 1 sooc to about + o o'
C, most preferably at a temperature of about 100° C. to about 230° C. This reaction can be carried out either under normal pressure or under pressurized conditions. If the operating temperature is below the boiling point of the reaction mixture, the reaction can conveniently be carried out at normal pressure. However, if the operating temperature is chosen above the boiling point of the reaction mixture, it is preferred to use a closed reactor or autoclave and to operate under autogenous pressure.

Suitable dehydrogenation catalysts for the process of the invention include platinum, 4 radium, rosium, ruthenium, iridium, nickel, gamma alumina, chromium oxide, molybdenum oxide, chromium oxide, molybdenum oxide, unsupported or on a suitable support. Contains tungsten, vanadium oxide, and rhenium. Typical catalyst supports include, for example, activated carbon, charcoal, silicon carbide, silica gel, alumina, acidic silica-alumina, silica, titania, norconia, kieselkuhl, mixed dilute ±1 oxides, carbonates, pumice, silica-alumina mixtures. , zeolite, etc. Suitable catalyst complexes may also be used, including M0 compounds (where M is pd or pt
-t or Ni, linked in the structure by a phosphine-straddling phosphite or carbamyl ligand).

Complexes of this type are generally soluble in the reaction mixture used in the process of the invention. Typical complexes include tetrakis(triphenylphosphine)platinum(0), bis[bis(
/,,2-diphenylphosphino)ethane]haladium(Q,bis[bis(i,,2-diphenylphosphino)
benzene]parazoum (0), tetrakis(triphenylphosphine)nickel(0), and tetrakis(triphenylphosphite)nickel(0).

The following examples are provided to further illustrate the invention and the manner in which it may be carried out. It will be understood, however, that the specific details shown in the examples are chosen for illustrative purposes only and are not intended to limit the invention. In the examples, unless otherwise specified, all parts and parts are by weight, and all temperatures are in °C.

Example 7 shows the production of fluorohexahydrophthalic anhydride and dark fluorohexahydrophthalic anhydride.

Example/Monel autoclave 7! 1 part of chlorotetrahydrophthalic anhydride was charged and cooled to about -30'C.

Add hydrogen fluoride to the Hirota section, seal the autoclave,
Heated to about 70″:C. Approximately ko/gθ~ri, deer q5K
q/d under autogenous pressure of about 2 d of pressure (60-65 psig). , S was kept at 70oC for one hour. Next, H.F.
was evacuated and the reactor was purged with N2. The liquid reaction product was dissolved in acetone, treated with sodium bicarbonate, and the acetone was removed by vacuum distillation. Analysis of the reaction products using gas chromatography techniques is based on starting materials of approximately S slag,
Hiro, 4! -Nofluorohexahydrophthalic anhydride 9/
, 7%, Hiro-chloro-danifluorohexahydrophthalic anhydride 0.7%, and Cuchlorotetohydrophthalic anhydride 0.6%.

Example Knee 3 The procedure of Example/ was repeated. However, the amount and conditions were changed as shown in the table below.

Example G SS to a reactor equipped with a cooling condenser and a stirrer,
O part cochlorotetrahydrophthalic anhydride and o, g
o parts of antimony pentachloride were charged.

The reaction mixture was stirred at normal pressure and at 23 to 1
Keep the temperature at Io0c\,3? , 6 parts of hydrogen fluoride were added over about 1 hour. The reaction mixture was kept under the same temperature and pressure conditions with stirring for an additional 11.2 hours. The hydrogen fluoride was then removed by evaporation over a period of approximately 2 hours. The reaction mixture was then mixed with about 4,! t
After heating to −70 cc and keeping at this temperature for about 2 hours, cooling to room temperature and analysis of the reaction products by t0 chromatography technique, q.

Kudifluorohexahydrophthalic anhydride g3. lI
%, 4-chlorohexahydrophthalic anhydride/H2, H-chlorotetrahydrophthalic anhydride 3.6%.

Example S-7 The procedure of Example A was repeated. However, the catalyst and conditions were changed as shown in the table below.

Examples g and 9 are /? Figure 2 shows the reaction of terdifluorohexahydrophthalic anhydride with basic alumina in the presence of radium on carbon. The reaction is /,,2. Hiroshi
It was carried out in liquid phase using trichlorobenzene. The reaction product is t due to the presence of radium in the reaction mixture.
- Contains t-fluorophthalic anhydride in addition to fluorotetrahydrophthalic anhydride.

Examples include a nitrogen introduction pipe, an air-cooled condenser, a submerged liver, and a magnetic 4Y5. 5. In a three-loaf flask equipped with a stirrer. + of θ1, <1-difluorohexahydrophthalic anhydride and 0.501 basic alumina and 20.0 Sg/, 2. Hiro - trichlorobenzene and 10 pieces of radium-supported charcoal were charged.

The contents of the flask were reduced to approximately 1/9 inch under a nitrogen atmosphere. ! t-
At a temperature of 2θθ℃? ,/hour of heating. Analysis of the reaction products using gas chromatography techniques revealed that Hiro-fluorotetrahydrophthalic anhydride (both isomers) was approximately lI2.
9%, Fluorophthalic Anhydride 3A, 2% Starting Material, 3T, Other Compounds/Z, 6%.

Actual example? Example g was repeated. However, the contents of the flask were varied by decreasing the relative ratio of basic alumina:starting material. The contents of the flask were as follows. 11. Hiro-difluorohexahydrophthalic anhydride/
, A P , basic alumina θ, og v, 5 chino or radium-supported carbon 3. θ1,/.

J, , 4(-)dichlorobenzene 15. The θJ0 flask was heated to approximately /q5~. under a nitrogen atmosphere. It was heated to a temperature of 20θ°C for 9.0 hours. Analysis of the reaction products using gas chromatography techniques revealed that fluorotetrahydrophthalic anhydride/λ, 6%, Hiro-fluorophthalic anhydride <1. ．． 2%, starting material 3, θ, and other compounds showed 2%.

Continued from page 1 Priority claim 01g8 group May 2nd [phase] United States (US)
[Phase] 604271 @ Inventor Jose A Poe 16 Cheektowaga Road, 14225 Lac, Iraq, New York, USA

Claims (1)

[Scope of Claims] +,+-dihalohexahydrophthalic anhydride of formula fi1 (in the above formula, Y is chlorine or fluorine). (2) The compound according to claim 1, wherein Y is chlorine. (3) The compound according to claim 1, wherein Y is fluorine. (4) Formula (in the above formula, Y is chlorine or fluorine) glue, Kudihalocyclohexane dicar? N city. (5) A compound according to claim 1, wherein Y is chlorine. (6) A compound according to claim 1, wherein Y is fluorine. (7) A method for producing a special glue, kudihalohexahydrophthalic anhydride, which comprises reacting hydrogen fluoride with kudihalohexahydrophthalic anhydride of the formula. The manufacturing method according to claim 7, characterized in that the molar ratio of f811(F:4t-chlorotetrahydrontalic anhydride is about to/:/ to about 2J:/. (91HF:4t - the ratio of chlorotetrahydroheptallic anhydride is about 2:/ to about:tS:/;
A manufacturing method according to claim 1, which has a W characteristic. 00) The process according to claim 7, characterized in that the process is carried out in a liquid phase at a temperature of about OCC to about /30°C. U. The manufacturing method according to claim 1O, which is carried out in a liquid phase at a temperature of about 200C to about 7θ. The manufacturing method according to claim 7, wherein a2 is carried out at approximately normal pressure. 03. The manufacturing method according to claim 7, characterized in that the manufacturing method is carried out under autogenous pressure. 8. The production method according to claim 7, which is carried out in the presence of a Lewis acid catalyst. (151) The manufacturing method according to claim 74, characterized in that the catalyst is antimony trifluoride. (16) Claim 74, characterized in that the catalyst is antimony trifluoride. The manufacturing method according to claim 11I. The manufacturing method according to claim 14', characterized in that the catalyst is molybdenum pentachloride. Anhydride (Formula 11. 1 II (in the above formula, Y is chlorine or fluorine), characterized in that it consists of reacting tadihalohexahydrontal acid anhydride with an effective amount of basic alumina. A method for producing a hydrated product of gou-fluorotetrahydrophthal MRhx having the formula: Cυ) The method according to claim 19, characterized in that Y is fluorine. The method of manufacturing according to claim 19. (2) The basic alumina is present in an amount of from about 3 to about 23 degrees rich in genohalohexahydrophthalic anhydride. (2) The basic alumina is present in an amount of from about 3 to about 23 parts by weight of the halohexahydrophthalic anhydride. The manufacturing method according to claim 2.2. (24J) The manufacturing method according to claim 19, which is carried out in a liquid phase at a temperature in the range of about 1SO°C to about core 00C. (c) Claim 19, characterized in that the process is carried out in a gas phase at a temperature in the range of about 200 cc to about 3θOOC.
Manufacturing method described in section. (c) The manufacturing method according to claim 19, wherein the manufacturing method is carried out under normal pressure. (27) The manufacturing method according to claim 1(d), characterized in that the manufacturing method is carried out under autogenous pressure. (281) A process for producing gou-fluorophthalic anhydride, characterized by heating gou-fluorohexahydrophthalic anhydride of the formula in the presence of an effective amount of a dehydrogenation catalyst. (2) In the liquid phase, about The manufacturing method according to claim 23, characterized in that the manufacturing method is carried out at a temperature of /left θ (~ about ≈ θθ). 6]) The manufacturing method according to claim 2g, characterized in that it is carried out in a gas phase. (32) It is carried out in a solvent. The manufacturing method according to claim 23, characterized in that (c) the manufacturing method according to claim 32, characterized in that the solvent is /, co, co-trichlorobenzene. ) The manufacturing method according to claim 2g, characterized in that the process is carried out at normal pressure. 09 The manufacturing method according to claim 2g, characterized in that the process is carried out at autogenous pressure. 66) The production method according to claim 23, wherein the catalyst is palladium-supported carbon.