WO2011123198A1

WO2011123198A1 - Methods for producing cycloheptatriene

Info

Publication number: WO2011123198A1
Application number: PCT/US2011/025646
Authority: WO
Inventors: Richmond M. Starrett; Christopher D. Claeboe; Anthony F. Skufca; Joseph H. Miller
Original assignee: Albemarle Corp
Current assignee: Albemarle Corp
Priority date: 2010-03-31
Filing date: 2011-02-22
Publication date: 2011-10-06
Anticipated expiration: 2012-09-30
Also published as: US20130066127A1; US8692042B2

Abstract

This invention relates to methods for producing cycloheptatriene from at least 7,7-dichloronorcarane and a liquid component comprising a C₈ to C₃₀ succinic anhydride, a carboxylic acid, or a C₈ to C₃₀ alkyldimethylamine at about 205 deg. C to about 230 deg. C.

Description

METHODS FOR PRODUCING CYCLOHEPTATRIENE

BACKGROUND

[0001] Cycloheptatriene is widely used as a ligand in organometallic chemistry and as a building block in organic syntheses. Known methods for producing cycloheptatriene, in particular methods using 7,7-dichloronorcarane as raw material, require high temperatures, usually in excess of 400 deg. C, and, thus, much energy for obtaining and maintaining the high temperatures and expensive equipment for surviving the high temperatures with repeated use.

[0002] Therefore, a need exists for improved methods for producing cycloheptatriene. THE INVENTION

[0003] This invention satisfies the above-defined needs by providing methods for producing cycloheptatriene comprising (a) combining at least 7,7-dich!oronorcarane and a liquid component in a container to form a reaction combination, wherein the container has a gas inlet and a gas vent, and the liquid component comprises a C₈ to C30 succinic anhydride, a carboxy!ic acid, or a CB to C3o a!kyldimethylamine; (b) while passing gaseous nitrogen through the reaction combination in the container via the gas inlet and the gas vent at a rate up to about 100 mL/min, heating the reaction

combination to, and maintaining the reaction combination at, about 205 deg. C to about 230 deg. C; (c) collecting distillate from the container; and (d) obtaining

cycloheptatriene from the distillate. This invention also comprises such methods wherein in (b) HCI is produced in the reaction combination and substantially all of the produced HCI is vented via the gas vent, and such methods wherein the distillate comprises substantially no 7,7-dichloronorcarane, e.g., less than about 1 vol%

7,7-dichloronorcarane, up to about 50 vol% 7,7-dichloronorcarane. Figures

[0004] The invention will be better understood by reference to the Figure (Figure 1 ), which illustrates a method according to this invention.

Description

[0005] The basic equation for CHT synthesis in accordance with this invention is as follows:

(succinic anhydride

or

carboxylic acid

7,7-

cycloheptatriene

[0006] C₈ to C-30 Succinic anhydrides suitable for use in methods of this invention include C_e to C₃₀ alkenyl succinic anhydrides, e.g., Ci₆ aikenyl succinic anhydrides. Ce to C₃₀ Alkyldfmethylamines suitable for use in methods of this invention include Ci₆ alkyldimethylamines. Suitable carboxylic acids for use in methods of this invention include long, short, and/or branched carboxylic acids. For example, cyclohexane carboxylic acid is suitable for use in this invention.

[0007] In methods of this invention, the reaction combination is heated to, and maintained at, about 205 deg. C to about 230 deg. C, or about 210 deg. C to about 225 deg. C, or about 215 deg, C to about 220 deg. C.

[0008] In methods of this invention, all, or substantially all, of the produced gaseous HCi is removed from the pyrolysis reaction in order to obtain CHT samples bearing minimized quantities of toluene while concomitantly increasing the isolated yield. In addition, the nitrogen purge is adjusted to such a rate as to effectively fiush HCI from the reaction combination while simultaneously minimizing 7,7-DCN from collecting in the distillate. Methods of this invention can be conducted under batch conditions or under semi-continuous conditions. In addition, vacuum distillation of the distillate from the container can be used to effect nearly complete removal of residual 7,7-DCN. EXAMPLES

[0009] The following examples are illustrative of the principles of this invention. It is understood that this invention is not iimited to any one specific embodiment exemplified herein, whether in the examples or the remainder of this patent application.

Example 1

[0010] To a 1000-mL, 4-neck round bottom flask fitted with a mechanical stirrer, nitrogen purge line and distillation condenser leading to a caustic scrubber was added 276.5 g of C16-ASA (C-|₆ alkenyl succinic anhydride) followed by 187.5 g (1.14 mol) of 7,7-dichloronorcarane. The stirred mixture was heated to approximately 220 deg. C under a slight nitrogen purge (1 -2 bubbles/sec observed in the scrubber). The distillate was collected as it was formed in the distillation adapter. After 9 hours, the reaction was allowed to cool. The cycloheptatriene thus obtained was isolated as a pale yellow liquid: crude yield 81.6 g (0.886 mol, 81.6%).

Example 2

[0011] A 3-L, 4-neck round-bottom flask 10 was equipped with a mechanical stirrer 20, thermocouple 5, nitrogen inlet 40, MASTERFLEX addition pump 50 and a distillation head 60 with associated distillate collection flask 70 and vent 65 (see the Figure (Figure 1)). The flask 10 was charged with 762 g C ₆-ASA followed by 605 g of 7,7-DCN via MASTERFLEX addition pump 50. The nitrogen sweep rate via nitrogen inlet 40 and vent 65 was set at approximately 100 mL/min and the mixture was heated to

approximately 215 deg. C. Once CHT collection in collection flask 70 was evident, the DCN addition via the MASTERFLEX addition pump 50 was continued at a rate of approximately 1.4 g/min. After 96-hr, the reaction was halted. Total processed

7,7-DCN was 5.4 kg resulting in a total of 2.2 kg crude CHT collected (73% crude yield).

[0012] , This invention is advantageous in that it provides methods for producing cycloheptatriene at temperatures of about 205-230 deg. C. or 210-225 deg. C, which is much lower than the temperatures of known processes, which require in excess of 400 deg. C. The benefits are that less energy is required to heat and maintain the temperature of the reactants and use of expensive equipment capable of withstanding the excessive temperatures of known methods is not required. Additionally, this invention facilitates the reduction of toluene formation by using a nitrogen sweep to eject the HCI by-product.

[0013] It is to be understood that the reactants and components referred to by chemical name or formula anywhere in the specification or claims hereof, whether referred to in the singular or plural, are identified as they exist prior to being combined with or coming into contact with another substance referred to by chemical name or chemicai type (e.g., another reactant, solvent, or etc). It matters not what chemical changes, transformations and/or reactions, if any, take place in the resulting mixture or solution or reaction medium as such changes, transformations and/or reactions are the natural result of bringing the specified reactants and/or components together under the conditions called for pursuant to this disclosure. Thus the reactants and components are identified as ingredients to be brought together in connection with performing a desired chemicai reaction or in forming a mixture to be used in conducting a desired reaction. Accordingly, even though the claims hereinafter may refer to substances, components and/or ingredients in the present tense {"comprises", "is", etc.), the reference is to the substance, component or ingredient as it existed at the time just before it was first contacted, combined, blended or mixed with one or more other substances, components and/or ingredients in accordance with the present disclosure. Whatever transformations, if any, which occur in situ as a reaction is conducted is what the claim is intended to cover. Thus the fact that a substance, component or ingredient may have lost its original identity through a chemicai reaction or transformation during the course of contacting, combining, blending or mixing operations, if conducted in accordance with this disclosure and with the application of common sense and the ordinary skill of a chemist, is thus wholly immaterial for an accurate understanding and appreciation of the true meaning and substance of this disclosure and the claims thereof.

[0014] While the present invention has been described in terms of one or more preferred embodiments, it is to be understood that other modifications may be made without departing from the scope of the invention, which is set forth in the claims beiow.

Claims

CLAIMS What is ciaimed is:

1. A method for producing cycloheptatriene comprising:

(a) combining at least 7,7-dichloronorcarane and a liquid component in a container to form a reaction combination, wherein the container has a gas inlet and a gas vent, and the liquid component comprises a C₈ to C₃o succinic anhydride, a carboxylic acid, or a C₈ to C₃o alkyldimethy!amine;

(b) while passing gaseous nitrogen through the reaction combination in the container via the gas inlet and the gas vent at a rate up to about 100 mL/min, heating the reaction combination to, and maintaining the reaction combination at, about 205 deg. C to about 230 deg. C;

(c) collecting distillate from the container; and

(d) obtaining cycloheptatriene from the distillate.

2. The method of claim 1 wherein the liquid component comprises a C₈ to C₃o alkenyl succinic anhydride.

3. The method of claim 1 wherein the liquid component comprises a Cie a!kenyl succinic anhydride.

4. The method of claim 1 wherein the liquid component comprises a carboxylic acid,

5. The method of claim 1 wherein the liquid component comprises a Ci₆ aikyidimethy!amine.

6. The method of claim 1 wherein in (b) HCI is produced in the reaction

combination and substantially all of the produced HCI is vented via the gas vent.

7. The method of claim 1 wherein the distillate comprises less than about 1 vol% up to about 50 vol% 7,7-dichloronorcarane.