KR820002082B1 - Process for preparing n-chloro imide - Google Patents

Abstract

Title compds. (I; R1,R2=H, =CH-CH=CH-CH=, III) were prepd. by N-chlorination of II by catalytic reaction with the mixt. of epoxy compds. and tertiary amines. Thus, Cl was introduced into a mixt.(0≰C) of phthalimide, 1,2-epoxybutane and 4-(dimethylamino)pyridine in CH2CI2, and the Cl-satd. mixt. was stirred 20 hr at room temp. to give N-chlorophthalimide.

Description

Method for preparing N-chloroimide

The present invention relates to a novel method for producing N-chloro imides of general formula (I), which has high use as a positive chlorine source in various organic reactions.

In the above formula

를 뜻한다.R ¹ and R ² are both hydrogen or R ¹ and R ² together are = CH-CH = CH-CH = or

It means.

An important conventional process for producing N-chloroimide uses an aqueous solvent system. In general, conventional methods for producing N-chloro imides can be classified as follows.

1) A method of chlorination of the corresponding imide using an inorganic hypochlorite in a mixture of acetic acid and water.

2) Chlorination through chlorine in an aqueous solution containing the same amount of the corresponding imide and strong bases such as sodium hydroxide and potassium hydroxide.

3) Chlorination of the corresponding imide using t-butyl hypochlorite in a mixture of t-butyl alcohol and water.

In the above general manufacturing method, only the production method (2) uses chlorine itself to prepare N-chloroimide. However, this method has serious disadvantages because it is a water-soluble medium. Firstly, it is widely known that chlorine is almost insoluble in water and, secondly, imides rapidly hydrolyze in alkaline aqueous media such as sodium hydroxide, potassium hydroxide and water.

More importantly, it has been found that N-chloro imide has the potential to decompose in an aqueous alkaline medium, such as under the chlorination conditions in preparation (2), to produce highly explosive, toxic nitrogen trichloride. Hurwitz, "Degradation of N-Chlorosuccinimidein Aqueous solution", Diss. Abst., B, 28 (3), 971 (1967).

There are few methods for preparing non-aqueous N-chloro compounds, and a method for preparing N-halo-t-alkyl cyanamides is described in US Pat. No. 2,686,203.

This method is a method of treating t-alkyl cyanamide with molecular chlorine in an inert solvent in the presence of an equivalent halogen acid acceptor such as pyridine.

Recently, a method of producing N-chlorophthalimide has been found under practically non-aqueous reaction conditions. According to this method, the alkali metal salt of phthalimide can be overcome with the above-mentioned disadvantages of using the aqueous alkaline medium by reacting the alkali metal salt of phthalimide with chlorine in the presence of a halogenated aliphatic hydrocarbon at a temperature of −10 ° to 40 ° C. (Belgium Kingdom Patent Application No. 853,686).

The present invention is directed to the corresponding imide with molecular chlorine in the presence of (1) an amount of epoxy compound equivalent to at least about 1 epoxy residue per individual amide residue and (2) at least a catalytic amount of tertiary amine under substantially anhydrous conditions. The contact feature provides a more convenient way to prepare N-chloroimide.

The Belgian patent application No. 853,686 mentioned above also acts on chlorine to the alkali metal salt of the imide, whereas the method of the present invention acts to chlorine on the imide. Excellent in

Furthermore, the present invention is characterized in that an imide having one or more of the following residues is contacted with chlorine molecules as described above.

More specifically, the present invention provides phthalimide, succinimide, glutarimide, 3,3-diethyl glutarimide, maleimide, "Δ ⁴ -tetrahydro phthalimide, 3, as described above. 4,5,6-tetrachlorophthalimide, pyromelliticimide, benzophenone tetracarboxylic diimide, naphthalene 1,4,5,8-tetracarboxylic diimide, chlorenidicimide, carbonyl Salicylicamide, dipenimide, tetrahydrofuran tetracarboxylic imide, 1,8-naphthalimide, or bicyclo (2,2,2) oct-7-ene-2,3,5,6- An imide, such as tetracarboxylic-2,3,5,6-diimide, is contacted with molecular chlorine to produce the corresponding N-chloro imides.

The present invention is convenient in that decomposition can be easily induced in the aqueous chlorination step and can be reacted with the imide itself rather than with the salt of the imide.

N-chloro imides, which are products of the present invention, have been known as effective reagents for reactions requiring a positive chlorine group. Examples of such reactions include oxidation of alcohols, sulfides, amines and imines, amines, reactive aromatic reaction systems, and chlorination of carbonyl or analog compounds with α-hydrogen. The literature describing these reactions is known as Al. Filler, Chem. Revs 63, 21 (1963) and al. Stroke, "Methoden der Organischen Chemie" (Houben-Weil), Vol. 5, Part 3, pp. 760-762, 796 et seq., Georg Thieme Verlag, Stuttgart (1962). Etc.

It has recently been found that penicillin sulfoxide can be converted to the corresponding 3-methylene sefamulfoxide by the following serial reaction.

This reaction is described in Kukolja et al., Journal of the American Chemical Society. 98, 5040 (1976) and described in more detail in Belgian Kingdom Patent No. 837,040. In the first step of the reaction, sulfenic acid is produced by heating, and the sulfenic acid is oxidized to obtain sulfinyl chloride. The sulfinylchloride is closed with 3-exomethylenecepam sulfoxide using Lewis acid reagents, especially tin chloride. In the preparation of sulfinylchloride, in particular N-chloroimide, it is necessary to use a positive chlorine reagent in the first step. Particularly preferred N-chloroimides according to Belgian patent number 837,040 include N-chlorophthalimide, N-chlorosuccinimide and N-chloroglutalimide.

In performing the penicillin sulfoxide reaction as described above, it is preferable to use N-chloroimide having several properties. First, it is desirable to use N-chloroimide which is not too large or small, i.e., N-chloroimide, which is stable and convenient to operate in order to proceed as desired. Secondly, it is preferable to use such N-chloroimides, in which the corresponding imides produced as by-products are sufficiently insoluble in the reaction system that can be readily separated off to easily separate the desired product.

New N-chloroimides that meet these properties are N, N-dichloro bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic-2, , 3,5,6-diimide.

As already mentioned above, the compound is (1) stable and sufficiently reactive to be used as a positive source of chlorine soon, and (2) diimide produced as a by-product is extremely low in solubility and can be easily separated and removed from the reaction medium. Therefore, it is very suitable to be used as a positive source of chlorine in the reaction reported by Cook Cole. The stability of this compound can also be seen by the fact that it dissolves only after being heated to 266 ° C or more. Moreover, the compound is unaffected even after toluene reflux for a considerable time, for example as long as 16 hours. Other more reactive N-chloroimides can be mixed with the solvent and left to react for some time at a fairly high temperature, causing at least some of the destruction. For example, N-chlorosuccinimide reacts with toluene (110 ° C., 16 hours) to produce the cyclic and α-substituents [C. Yavoslavsky and E. Katchalski, Tetrahedron Letters, 51, 5173 (1972).

Furthermore, the compounds represented by the formula (I ') are usually very readily soluble in the organic solvents used to carry out the positive base reactions and this reaction occurs. As an example, the solubility in boiling toluene is very high, approximately 3 g / l, but diimide, a byproduct of the positive chlorine reaction, is almost insoluble and can thus be easily removed from the reaction system. In other words, the solubility of this diimide in boiling toluene is less than 25 mg / l, and further, the by-product diimide is in a crystalline state with a very stable melting point above 410 ° C.

Structural formula (I ') compounds are very advantageously removed by the novel methods described herein. However, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5,6-diimide can also be prepared by chlorination by conventional methods. .

The conventional method for such N-chlorination is to di-imide the diimide with molecular chlorine in acetic acid in the presence of acetate as indicated in Example 15 below. This reaction takes place effectively under temperature conditions between 0 ° C and about 80 ° C.

Chlorination to prepare the compound of formula (I ′) can also be carried out using other conventional N-chlorinating agents. Among them, hypochlorite is the most widely known and commonly used. In particular tertiary butyl hypochlorite is used and alkali metal hypochlorites such as hypochlorite of sodium or calcium have also been commonly used as conventional N-chlorinating agents. In addition, other conventional conventional N-chlorination methods may be used to prepare the compound of formula (I '). For example, 1-chloro benzotriazole is suitable, and chloro isocyanuric acid is also used as the N-chlorinating agent. do.

As for the method of manufacturing such N-chloroimides, Al mentioned above. Straw and Egg. Filler's literature has another reference. Oelschlaeger et al., Pharm. Acta Helv. 47, 1-6 (1972); Matsushim et al., Biochim. Biophys Acta. 271, 243-51 (1973); and Cinquini et al., Synthesis) 1972, 259-60.

N-chlorination agents commonly used as described in the prior art as described above is highly effective when used in the chlorinated aliphatic or aromatic solvent or solvent of the aqueous reaction system to be described later. In general, the reaction temperature is effective from 0 ℃ to 5 ℃ and usually used. As described above, the present invention relates to a process for producing N-chloroimide, and also includes a process for producing a desired N-chloroimide by interaction of a corresponding imide with molecular chlorine under substantial anhydrous support. .

The reaction defined in the present invention is an equivalent reaction in the sense that one mole of chlorine is consumed with respect to one mole of imide. Therefore, it is highly desirable that at least one mole of chlorine be present for each mole of imide moiety and the preferred condition is to use an excess of 10% chlorine.

The reaction temperature is not so important but generally runs between -10 ° and 50 ° C, preferably between -5 ° and 25 ° C. The reaction is mostly terminated after 1 to 24 hours and is preferably carried out over 3 to 15 hours.

The main feature of the present invention is that the reaction can occur under substantially anhydrous conditions.

The term "substantially anhydrous condition" does not mean that there is no water in the reaction system, but rather does not intentionally add water before or during the reaction. The water normally contained in commercial solvents or reactants used in the reaction process of the present invention does not need to be removed deliberately. Generally, the amount of water in the reaction mixture is about 0.2%.

Although not critical in the present invention, there is also a method of proceeding the reaction in the presence of an inert organic solvent. The term "solvent" refers to a medium capable of partially or completely dissolving the starting material imide, and the term "inert solvent" refers to a solvent that does not react with the reactants, mainly chlorine, under the production reaction conditions. Typical these inert solvents are halogenated aliphatic and aromatic hydrocarbons. Examples of halogenated aromatic hydrocarbons include chlorobenzene, 1,2-dichlorobenzene, 1,4-dichlorobenzene, bromobenzene and the like. Examples of halogenated aliphatic hydrocarbons include methylene chloride, chloroform, 1,1,2-trichloroethane, 1,2-dichloroethane, 1,1-dichloroethane, 1,1.1-trichloroethane and the like. Of these, halogenated aliphatic hydrocarbons are preferred, of which a suitable solvent is methylene chloride.

Starting material imides used in the preparation of the present invention can be broadly defined as diacylamine compounds, and in particular, compounds containing one or more of the following moieties.

These imides are preferably free from other functional groups reactive under the reaction conditions of the present invention. Typical functional groups which should be absent are ether, epoxy, hydroxy, amino, sulfide, sulfoxide, carboxyl and activated methylene as well as other functional groups having at least one acidic hydrogen group.

Particularly suitable imides suitable for the production process of the present invention include phthalimide, succinimide, glutimide, 3,3-dimethylglutalimide, maleimide, "Δ ⁴ -tetrahydrophthalimide, 3, 4,5,6-tetrachlorophthalimide, pyromelliticimide, benzophenone tetracarboxylic diimide (1)

Naphthalene 1,4,5,8-tetracarboxylic diimide (2)

And bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5,6-diimide.

The above has been shown for the purpose of description only, and has shown about various wide range imides (including polyimide) suitable for the manufacturing process of this invention. Imides particularly suitable for the process of the invention are phthalimide, succinimide and bicycl [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3, 5,6-diimide. The most suitable imide among them is phthalimide and bicyclo- [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5,6-diimide.

In addition to molecular chlorine and imide, which are the main reactants, the present invention uses a catalyst and an acid remover. Catalysts and acid removers are believed to work cooperatively to effectively remove hydrogen chloride produced as a by-product when molecular chlorine and imides react during the manufacturing process of the present invention. The catalyst acts as a medium to ensure that the hydrogen chloride produced as a by-product is well selected by the acid scavenger, which is believed to act as the ultimate scavenger of hydrogen chloride.

The acid remover used in the present invention is an epoxy compound. The epoxy compound is present at least equivalent to the imide content of the starting material. As used herein, the term "equivalent" means that at least one epoxy residue is present for each individual imide residue. Excess epoxy compound may be used. However, in an economic sense, it is appropriate to use an epoxy compound of 1.1 to 5 times the equivalent value for the imide compound. More preferably, it is preferable to use an epoxide compound having a residue as shown in the figure below, ie, a terminal epoxide group.

Examples of typical epoxy compounds include ethylene oxide, propylene oxide, 1,2-epoxybutane, butadiene diepoxide, 1,2-epoxy-3-phenoxypropane, 1,4-butanediol-diglycidyl ether, 1, 2,7,8-diepoxyoctane. Most preferred epoxy compounds are propylene oxide and 1,2-epoxybutane.

The catalyst is used in combination with an acid scavenger in an amount of 0.01 to 0.04 molar equivalents relative to the imide moiety equivalents of the starting material imide. It may be used in large quantities. The catalyst used in the present invention uses a compound having the structure of a tertiary amine so as to easily act as a "catalyst carrier". The term "catalytic carrier" refers to a tertiary amine used to remove hydrogen chloride produced as a by-product from the protonated N-chloroimide intermediate to an acid remover to react with the acid remover and remove from the reaction system. Tertiary amines such as these are compounds having characteristics that make it easy to deprotonate the protonated N-chloroimide intermediate to produce hydrochloride. The resulting hydrochloride is easily solubilized in the reaction system because of its high solubility in the reaction system and at the same time unstable, so the reaction with the acid remover also occurs easily. Accordingly, tertiary amine catalysts possess the following characteristics.

(1) Has the ability to produce its own hydrochloride by reacting with quantized N-chloroimide intermediates.

(2) generates a hydrochloride that is at least partially dissolved in (a) the reaction medium, and (b) is unstable and reacts with an acid scavenger with the ability to remove hydrogen chloride and re-release free tertiary amines.

Typical tertiary amines suitable for the present invention include 1,5-diazabicyclo- [4,3,0] -non-5-ene (DBN), 1,5-diazabicyclo- [5,4,0]- Undec-5-ene (DBU), pyridine, 1,8-bis (dimethylamino) naphthalene, 4-dimethylaminopyridine, N, N-dimethylbenzylamine, diisopropylethylamine, quinoline, 2,4,6- Trimethylpyridine, pyrimidine, pyrazine and the like. In general, structural derivatives of pyridine comprising pyridine or quinoline are preferably used as catalysts in the present invention. Pyridine and quinoline are particularly preferred.

Representative methods for preparing N-chloroimide according to the present invention are as follows.

Phthalimide (0.6 mole) is slurried in methylene chloride (up to about 1.7 liters) and cooled to 5 ° C. 1,2-epoxybutane (3.0 moles) and quinoline (0.006 moles) are added. A sufficient amount of chlorine in the gas or liquid phase (approximately 0.66 moles) is injected below the surface of the slurry through the feed tube. The cooling bath is removed and the reaction mixture is warmed to a temperature no higher than approximately 25 ° C. After 1 to 3 hours, the starting material, phthalimide, is almost lost or completely lost, and the reaction solution gradually becomes transparent to become a yellow solution. After a few minutes of partial depressurization to remove excess chlorine, add amylene (2-methyl-2-butene) to remove all remaining chlorine, and the straw-colored reaction mixture remains. Some exothermic reactions are observed when amylene interacts with excess chlorine. Excess 1,2-epoxybutane and methylene chloride are removed in vacuo at a temperature not exceeding 25 ° to 30 ° C. As the solvent is removed, the product N-chlorophthalimide precipitates in the crystalline phase. Reducing the volume of the reaction solution to 130 to 150 ml mainly consists of the product and butylene chlorohydrin. The reaction solution was filtered by ice cooling for 1 hour, and then the collected product was washed with a small amount of cold toluene or petroleum ether. The product is dried under reduced pressure at 25 ° C. for 18 hours to yield colorless to white granular crystalline powder in 92 to 96% yield.

The following examples merely illustrate the preparation of the invention and are not intended to be limiting.

Example 1

In 150 ml of methylene chloride, 7.35 g (0.05 mol) of phthalimide, 21.5 ml (5 equivalents) of 1,2-epoxybutane, 0.061 g (0.5 mmol) of 4-dimethylaminopyridine were added and the mixture was stirred at 0 ° C. After cooling to saturation with chlorine. The mixture was stirred for 20 hours at room temperature, and a sample of the reaction mixture was taken and analyzed by thin layer chromatography (TLC), indicating that the reaction was not completed. The mixture is further stirred for 24 hours, and the resulting clear yellow solution is evaporated to give N-chlorophthalimide as crystals. Drying in vacuo afforded 7.7 g (84.8%) of product.

Assay: (%) Cl ⁺ : Theoretic: 19.6; Found: 18.3 (%) Total Chlorine: 18.1

Melting Point: 183 ~ 189 ℃

Example 2

7.35 g (0.05 mole) of phthalimide and 17.5 ml (5 equivalents) of propylene oxide are added to 150 ml of methylene chloride, the mixture is cooled to 0 ° C., and 0.13 g (0.001 mole; 0.02 equivalents) of quinoline is added. The mixture is then saturated with chlorine. Phthalimide starts to dissolve within 30 minutes and almost dissolves after 1 hour. TLC analysis after 1.25 hours showed that only the traces of the starting material remained. Partial vacuuming removes excess chlorine, small amounts of amylene is added, and the resulting mixture is evaporated to yield crystals of N-chlorophthalimide. Filtration of the product and drying under vacuum overnight yielded 8.2 g (90.4%) of the same product as in Example 1.

Assay: (%) Cl ⁺ : Theoretic: 19.6; Found: 19.3 (%) Total Chlorine: 19.1

Example 3

The same reaction as in Example 2 was carried out using 0.08 g (1 mmol; 0.02 equivalent) of pyridine as a catalyst. After 1.5 hours, the reaction was completed, and 8.0 g (88.2%) of N-chlorophthalimide as in Example 1 was obtained.

Assay: (%) Cl ⁺ : Theoretic: 19.6; Found: 19.2 (%) Total Chlorine: 19.0

Example 4

0.12 g (1 mmol; 0.02 equiv) of 2,4,6-trimethylpyridine was used for the same reaction as in Example 2. After 2 hours the reaction was complete, yielding 8. lg (89.3%) of N-chlorophthalimide as in Example 1.

Assay: (%) Cl ⁺ : Theoretic: 19.5; Found: 18.0 (%) Total Chlorine: 17.2

Example 5

The reaction as in Example 2 was carried out using 0.08 g (1 mmol: 0.02 equivalent) of pyrimidine. After the completion of the reaction after 2 hours, 8.5 g (93.7%) of N-chloro phthalimide as in Example 1 was obtained.

Anal: Cl ⁺ : Theory: 19.5; Found: 19.3 Total Chlorine: 19.0

Example 6

9.9 g (0.1 mole) of succinimide is added in 300 ml of anhydrous methylene chloride. To the resulting slurry was added 35 ml (5 (5 equivalents) of propylene oxide and 0.12 g (1 mmol) 4-dimethylaminopyridine, then cooled to 0 ° C. and saturated with chlorine The mixture was stirred for 18 hours while warming to room temperature Taking a sample of the reaction mixture and performing TLC showed little starting material, evaporation of the solvent and cooling of the residue gave crystals of N-chlorosuccinimide. After filtration, collecting, washing with a small amount of toluene and vacuum drying yielded 10.6 g (79.4%) of the primary crop.

Analysis (%): Cl: Theoretic: 26.6; Found: 26.3 (%) Total Chlorine: 25.9

1.25 g (9.4%) of secondary hydrate are obtained.

Anal (%) Cl ⁺ : Theoretic: 26.6; Found: 25.4 (%) Total Chlorine: 25.l Melting Point: 144 ~ 147 ℃

Example 7

7.35 g (50 mmol) of phthalimide and 17.5 ml (250 mmol) of propylene oxide are added to 150 ml of anhydrous ethylene chloride, followed by cooling to 0 ° C. and 0.1 lg (0.5 mmol) of l, 8-bis (dimethylamino) Add naphthalene. When excess chlorine was added, the mixture became a bright orange color. It is stirred overnight at room temperature (about 16 hours) and the solvent is evaporated under vacuum. Water was added to the obtained crystalline residue, the mixture was filtered, and the solids were collected and washed with a large amount of water to obtain 8.9 g (98.1%) of the same N-chlorophthalimide as in Example 1.

Anal (%) Cl ⁺ : Theoretic: 19.5; Found: l9.1 (%) Total Chlorine: 18.6

Example 8

Example 8 using 0.08 g (0.5 mmol) of 1,5-diazabicyclo [5,4,0] undec-5-ene (DBU) instead of 1,8-bis- (dimethylamino) naphthalene Proceed with the same reaction. The same product N-chlorophthalimide (8.42 g: 92.8%) as in Example 1 is obtained.

Anal (%) Cl ⁺ : Theoretic: l9.5; Found: 17.4 (%) Total Chlorine: l6.9

Example 9

7.35 g (0.05 mole) of phthalimide and one drop of DBU are added in 150 ml of methylene chloride followed by one equivalent of 1,2-epoxy-3-phenoxy propane. When this mixture is reacted, N-chlorophthalimide is obtained.

Example 10

When the reaction was carried out according to Example 9 using 0.07 g (0.5 mmol) N, N-dimethyl benzylamine instead of DBU, 8.5 g (93.7%) of N-chlorophthalimide was obtained as in Example 1. Lose.

Anal (%) Cl ⁺ : Theoretic: 19.5; Found: 16.3 (%) Total Chlorine: 16.7

Example 11

88.2 g (0.6 mole) phthalimide, 210 ml (5 equivalents) of propylene oxide and 0.75 g (6 mmol) of 4-dimethylamino pyridine are added in 1700 ml of methylene chloride and the mixture is cooled to 0 ° C. and excess Add chlorine. The mixture is stirred for a total of 8 hours and 5 ml of amylene are added. The mixture is evaporated under vacuum to give l25 ml to crystallize. The mixture is cooled in ice for 1.5 hours and filtered. The product was collected, washed with a small amount of toluene and dried in vacuo overnight to give 103.6 g (95.1%) of the same product N-chlorophthalimide as in Example 1.

Anal (%) Cl ⁺ : Theoretic: 19.5; Found: 19.1 (%) Total Chlorine: 19.5

Example 12

7.35 g (0.05 mole) of phthalimide in 150 ml of anhydrous methylene chloride followed by 17.5 ml (5 equivalents) of propylene oxide and 0.065 g (0.5 mmol) of diisopropyl ethylamine are then cooled to 0 ° C. and chlorine Saturate with. Stirring this mixture for about 24 hours converts about 50% to N-chlorophthalimide.

Formulation Method 1

1007.5 g (4.06 mole) of bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5,6-dianhydride in 200 ml of formamide And add ammonia while heating the mixture. (Ammonia is added at high speed as it is absorbed in the reaction mixture). An exothermic reaction occurs. The initial temperature of the mixture is 40 ° C. but rises to 140 ° C. after 7 minutes. When the product falls to the crystals, the operation of adding ammonia is stopped and the solvent is distilled off. When 1.75 hours have elapsed, the temperature of the reaction mixture rises to 178 ° C., and when 3.75 hours is reached, 180 ° C., 130 ml of distillate is collected. The heating is stopped and the reaction mixture is cooled under vacuum distillation. After 30 minutes, the temperature of the mixture drops to 90 ° C. Stop vacuum distillation and dilute the reaction mixture with approximately 2000 ml of acetone. The mixture was cooled in an ice bath to 5 ° C., filtered and the product was collected, washed with acetone and dried to give 907.9 g of (90.8%) bicyclo [2,2,2] oct-7-ene-2,3, 5,6-tetracarboxylic-2,3,5,6-diimide is obtained.

Example 13

246.2 g (1 water) of bicyclo [2,2,2] oct-7-2,3,5,6-entetracarboxylic-2,3,5,6-diimide, 600 ml in 1000 ml methylene chloride Propylene oxide, and 4.7 ml (0.04 mol) quinoline were added. The mixture is cooled to 20 ° C. and chlorine is added at a controlled rate while cooling with ice so that the reaction temperature is maintained between 20 ° and 30 ° C. After about 40 minutes the mixture becomes dense, reducing the rate of chlorine addition, and further reducing the rate after about 2.5 hours and gently stirring overnight at 25 ° to 30 ° C. In the morning, the reaction mixture became white (25 ° C). The rate of chlorine addition is increased and the temperature rises to 30 ° C. after about 2.5 hours. The operation of adding chlorine is stopped and concentrated in vacuo to remove excess propylene oxide and chlorine. After about 25 minutes, when the temperature drops to 5 ° C., the reaction mixture is quickly filtered and the filter cake is washed with 500 to 1000 ml of methylene chloride, ether, toluene and pentane in that order. The filter cake was air-dried for five to six hours and the solid dried further under vacuum at 40 ° to 50 ° C. overnight to give 308.4 g of N, N-dichlorobicyclo [2,2,2] oct-7-ene-2,3, 5,6-tetracarboxylic-2,3,5,6-diimide is obtained. Melting Point: 266 ° C (Decomposition Point)

Anal (%) Cl ⁺ : Theoretic: 22.5; Found: 21.7

Some methylene chloride is present in the product, which can be removed by refluxing the N-chloroimide in toluene.

Example 14

In a 1 L flask, 125 g (part of total weight 267.7 g) of 170.6 g of phthalimide were added cold 1,2-epoxy butane and 2.3 g of quinoline. The mixture is cooled to 13 ° C., stirred and chlorine is added through the tube below the mixture surface. About 56 g of chlorine is added over 1.5 hours while maintaining the temperature of this mixture at 13 ° to 15 ° C. During chlorine addition, the mixture initially becomes cloudy and then becomes cloudy.

The operation of adding chlorine is stopped and 96 g of phthalimide is added to the mixture. Start adding chlorine again while maintaining the temperature between l4 and 15 ° C. 40 g of chlorine is added over 0.75 hours and the mixture becomes cloudy. The operation of adding chlorine is stopped and the remaining phthalimide (267.7 g total) is added to this mixture. Start adding 30 g of chlorine over 0.5 hour while maintaining the temperature between 12 ° and 15 ° C.

This mixture is warmed to 21 ° C. over about 0.5 hour. Taking a small amount of samples and performing thin layer chromatography (TLC), the analysis shows that there is some unreacted material. The mixture is cooled to 12 ° C. and 6.5 g of chlorine are added. The mixture was again warmed up and filtered to give 322.4 g of the product N-chlorophthalimide as in Example 1.

Analysis (%) Cl ⁺ : Theoretic: 19.5: Found: 18.7

Example 15

369 g of sodium acetate dissolved in 369 g of bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5,6-diimide in 1500 ml of acetic acid Stir together under chlorine atmosphere. The temperature is kept at 40 ° C. while cooling for 1 hour. The temperature is lowered to 32 ° C. and the sides of the flask are washed with a small amount of acetic acid. The reaction mixture is heated to 60 ° C. and stirred through a gas until chlorine is saturated. Stop heating and gas injection and stir for 2 more hours. The temperature at the reaction end point is 27 ° C. The flask is washed with 300 ml of methylene chloride and cooled in an ice bath. After 25 minutes 2500 ml of ice water is added to the mixture (5 ° C.), the mixture is filtered and the solid is washed with 1500 ml of water and 1500 ml of methylene chloride. The product was dried in a vacuum desiccator to a temperature of 30 ° to 40 ° C. to give the same product N, N'-dichlorobicyclo [2,2,2] oct-7-ene-2,3,5 as in Example 14. , 6-tetracarboxylic-2,3,5,6-diimide is obtained.

Example 17

A portion of bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5,6-diimide is dissolved in methylene chloride and tert-butyl hypo Add chlorite and stir the mixture for 16 hours. The reaction mixture was vacuum dried to yield crude N, N'-dichlorobicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic-2,3,5. , 6-Diimide is obtained, which is purified by recrystallization to give the same pure product as in Example 14.

Claims (1)

Contacting the corresponding imide of formula (II) with molecular chlorine in the presence of at least about one epoxy residue equivalent to at least about one epoxy residue per individual imide residue under substantial anhydrous conditions and at least a catalytic amount of tertiary amine Characterized in that the N-chloroimide of formula (I) is prepared.

In the above formula R ¹ and R ² are both hydrogen, or R ¹ and R ² together are CH = CH = CH-CH = or

Means, R ¹ 'and R ² ' are both hydrogen, or R ¹ 'and R ² ' together are = CH-CH = CH-CH or

It means.