DE1178421B - Process for the production of asymmetrical imidocarbonic acid-bis-esters - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Boarding school Cl .: C 07 c;

C07d

German class: 12 ο-22

Number: 1178421

File number: F 39155IV b / 12 ο

Filing date: March 2, 1963

Opening day: September 24, 1964

The invention relates to a process for the production of asymmetrical aromatic imidocarbonic acid bis-esters the general formula

NH

R - Ό - C

• ο — IR '

Ix

where χ = 1 to 6 and R and R 'can be any aromatic or heterocyclic radicals different from one another.

Asymmetrical imidocarbonic acid esters have not yet been described in the literature.

A process has now been found for the preparation of the compounds mentioned, which thereby is characterized in that an aromatic or heterocyclic cyanic acid ester with an aromatic or heterocyclic hydroxy compound is reacted in the presence of a base. One can here both

Process for the preparation of asymmetrical imidocarbonic acid bis-esters

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen

Named as inventor: Dr. Ernst Grigat, Köm, Dr. Rolf Pütter, Düsseldorf

where χ = 3 and y = 1, one can use 1 mol

OCN

y R - (OCN) ₃ : with χ R '- (OH) ₂ ,

as well as

each R '- (OCN) ₁ , with y R - (OH) ₂₁ with 3 mol

OCN

where either χ = 1 and y = 1 to 6 or y = 1

and χ = 1 to 6, to the compounds mentioned 30 as well as 3 mol

realize. In the simplest case this means,, . ^

that <i V-OCN

NH
R —Ο —C —Ο —R 'with 1 mole

OH

can be made from ROC = N and R'-OH or R-OH and R'-OC = N.
If, for example, R is a phloroglucyl radical OH

OH

to the imidocarbonate

NH

and R 'is a phenyl radical

realize.

The cyanic acid esters can, according to a suitable older proposal, by reacting phenols

409 688/385

3 4

with halogen cyanides at temperatures below class a characteristic band at 5.9 to 6 μ

65 ° C in an inert organic medium.

Presence of an organic base can be produced. _R. . ,.

As cyanic acid esters, inter alia, a P

are set: phenyl cyanate, mono- and poly- 5 4 g 4-methylphenyl cyanate and 3.7 g 2,4-dimethylalkyl-phenyl cyanate, Arylphenyl cyanates and dialkyl phenol are dissolved in 10 ml of acetone. In the aminophenylcyanate, acylaminophenylcyanate, Ni addition of 0.1 g of solid NaOH with thorough stirring

trophenylcyanate, halophenylcyanate, cyanato- at room temperature the temperature rises

phenylcarboxylic acid, esters, amides, Cyanatophenyl- solution to about 45 ⁰ C to. It is heated briefly to

sulfonic acids, esters, amides, alkoxyphenyl cyanates, boiling point of acetone and allow to cool.

Phenoxyalkylcyanate, Acyloxyphenylcyanate, Acyl- It is filtered off from little precipitated, from

phenylcyanate, cyanophenylcyanate, naphthalene filtrate, the acetone stripped off in vacuo and so

cyanate, anthraquinone cyanate, quinone cyanate, chi- as residue of O- (4-methylphenyl) -O '- (2,4-di-

nolincyanate, phenylenedicyanate, naphthylenedicymethylphenyl) -imidocarbonic acid-bis-ester as pale

anates, tricyanatobenzenes, biscyanatodiphenylme- 15 oil obtained. The IR spectrum shows a strong one

thane, alkenes. Band between 5.9 and 6 μ.

As phenols, among other things, the on- The crude product is used for purification in ether

counted cyanates used analogous phenols added, the ethereal solution with aqueous

will. NaOH shaken, the phases are separated, the

The reaction can in a liquid medium 20 is dried with CaCU and the ether solution be performed. As a solvent, ethers are drawn off in vacuo. The purified pros as well Water and organic solvents are left behind. Yield: 6.0 g (= 78% such as alcohols, ethers, ketones, aromatic and ali- theory). The product remains even after cleaning phatic - optionally halogenated or oily. During distillation, decomposition occurs in the in nitrated - hydrocarbons. Here are the 25 ways indicated in the note. The raw material named for example: ethanol, diethyl ether, unpurified product can be used for further implementation Acetone, benzene, mineral spirits, carbon tetrachloride are used, and nitrobenzene.

Both inorganic and Example 2

organic bases act, e.g. B. Alkali hydroxides 3 °

or amines. In a solution of 4.88 g of 2,4-dimethylphenol

For example, the following bases and 1.8 g of NaOH in 30 ml of water can be 5.32 g

are used: sodium hydroxide, triethylamine, 4-methylphenylcyanate added dropwise. The solution

Diethylaniline, diisopropylmethylamine. warms up and is stirred for some time, then

To carry out the reaction one can shake out 35 with ether, the ether phase with aqueous washed the cyanate NaOH in a liquid medium, dried with Na2SÜ4 and submit and the hydroxy compound and one finally the ether evaporated. It remains that Add base, but you can also use the hydroxy-O- (4-methylphenyl) -O '- (2,4-dimethylphenyl) imido compound Submit and add cyanate and base, carbonic acid-bis-ester back as a light oil. That Submit cyanate and hydroxy compound and the 40 IR spectrum of the substance is identical to that Add base, submit cyanate and base and add those of the product from Example 1. Hydroxy compound and finally hydroxy compound and base and add the cyanate example 3. One can also use the cyanate with the alkali salt convert a hydroxy compound. 45 In a solution of 7.0 g of sodium phenolate in

The reaction can be carried out in a temperature range 50 ml of water, 4 g of 1,3,5-tri-

from 0 to 100 ⁰ C, preferably between 0 and 50 ° C, entered cyanatobenzene. Warming occurs

be performed. on. An oily solid product precipitates out in ether

The base should be added in amounts of 0.01 to 1 mol and purified as in Example 1,

based on the hydroxy compound, to be present, 5 ° Das
Cyanate and hydroxy compound in molar ratio

^{1: L} / NH For isolating the asymmetrical imido carbon

acid-bis-ester is optionally supported by solid back-

was filtered, the solvent and the base removed.

distilled and the remaining imidocarbonic acid-bis-ester purified if necessary.

The compounds obtained are new and remain as a yellow oil that slowly crystallizes as starting materials for manufacture. Yield: 7.5 g (= 77.5% of theory), used from drugs and textile auxiliaries ^ ⁰ IR spectrum: strong band at 5.9 to 6 μ. will.

Most Unsymmetrical Imidocarbonic Acids - Example 4

bis-esters are oils, some of which are more or less

crystallize quickly. During distillation To 1.25 g of phloroglucinol dissolved in 25 ml of acetone,

if they decompose with the formation of triazine derivatives ⁶ 5, with vigorous stirring, 4.0 g are simultaneously obtained with elimination of phenols. You can pour in the 4-methylphenyl cyanate and 4.35 ml of triethylamine to form an imidocarbonic acid bisester. The temperature rises to 25 to 30 ⁰ C on the IR spectrum recognize, since this connection to. After stirring for 10 minutes, acetone is added

and amine stripped off in vacuo at room temperature. That

/ NH

C ₆ H ₃

O — C —O

CH ₃

remains as a syrupy, yellowish oil. Yield: 4.7 g = 89% of theory. IR spectrum: strong band at 5.9 to 6 μ.

Example 5

To a solution of 4.5 g of 2-methoxyphenyl cyanate in 20 ml of acetone, 2.8 g of phenol, dissolved in 15 ml of acetone, and 4.35 ml of triethylamine are added simultaneously at room temperature. The temperature rises to about 25 to 30 ^° C. After the acetone and amine have been stripped off, 7 g (= 95% of theory) of the O-phenyl-O '- (2-methoxyphenyl) -imidocarbonic acid bis-ester remain as a clear, light oil, which crystallizes through to a white crystalline mass. Purification is not necessary for further reactions, but can be carried out as in Example 1. IR spectrum: strong band at 5.9 to 6 μ.

Example 6

Analogously to Example 5, the O-phenyl-O '- (3-chlorophenyl) -imidocarbonic acid bis-ester is obtained as a yellowish, waxy crystalline mass from 3-chlorophenyl cyanate and phenol. Yield: 94% of theory. IR spectrum: strong band at 5 _; 9 to 6 μ.

Example 7

As in Example 5, 2,4-dimethylphenyl cyanate is obtained and phenol the O-phenol-O '- (2,4-dimethylphenyl) -imidocarbonic acid-bis-ester as a light, volatile oil. Yield: 90% of theory. IR spectrum: strong band at 5.9 to 6 μ.

Example 8

Analogously to Example 5, 1 mole of p-phenylene dicyanate is obtained 2 moles of phenol and triethylamine in acetone

NH
PC ₆ H ₄ O-COC ₆ H ₅ J

with a melting point of 120 ^° C. in 86% yield. IR spectrum: strong band at 5.9 to 6 μ.

Example 9

that slowly crystallizes through. IR spectrum: band at 5.9 to 6 μ.

Example 11

Analogously to Example 5, 2,6-diethylphenyl cyanate is obtained and 4-chlorophenol denotes O- (2,6-diethylphenyl) - O '- (4 - chlorophenyl) - imidocarbonic acid - bisester as a water-clear oil. IR spectrum: strong band at 5.9 to 6 μ.

Example 12

Analogously to Example 5, the O- (4-nitrophenyl) -O ^/ - (4-chlorophenyl) -imidocarbonic acid-bis-ester is obtained from 4-nitrophenylcyanate and 4-chlorophenol as a yellow, initially oily, then crystallizing substance with a temperature of 98 bis 104 ° C. IR spectrum: strong band at 5.9 to 6 μ.

Example 13

Analogously to Example 5, 3-Οι1θφ1ιε ^ 1-cyanate is obtained and 4-Οι1οφ1ιεηο1 the O7 (3-chk ^ henyl) -O ' - (4 - chloφhenyl) - imidocarbonic acid - bis - ester as yellow oil that soon crystallizes through. M.p. 84 to 85 ° C; IR spectrum: strong band at 5.9 to 6 μ.

Example 14

Analogously to Example 5 is obtained from 2,6-diethyl

phenylcyanate and 4-nitrophenol denote Ö- (2,6-diethylphenyl) - O '- (4 - nitrophenyl) imidocarbonic acid bisester as a dark oil interspersed with crystals. IR spectrum: strong band at 5.9 to 6 μ.

35

40

45

55

Analogously to example 5 one obtains from /? - naphthyl cyanate and p-cresol the O- (naphthyl-2) -O '- (4-methylphenyl) -imidocarbonic acid-bis-ester as a white, crystalline substance that changes when it melts. IR spectrum: band at 6.05 µ.

Example 10

Analogously to Example 5, the O- (quinolino-5) -O '- (4-methylphenyl) -imidocarbonic acid bis-ester is obtained from 5-cyanatoquinoline and p-cresol as yellow oil,

Example 15

Analogously to Example 5 is obtained from 3-Chloφhenylcyanat and 4-nitrophenol denotes the O <3-Chloφhenyl) -O ' - (4 - nitrophenyl) - imidocarbonic acid - bis - ester as a yellow oil that soon crystallizes through. IR spectrum: Strong band at 5.9 to 6 μ.

Example 16

Analogously to Example 5, the O- (4-acetylphenyl) -O ^/ - {2,4-dichlorophenyl) imidocarbonic acid bisester is obtained from 4-acetylphenyl cyanate and 2,4-dicluorophenol as a light brown oil which slowly crystallizes through. IR spectrum: strong band at 5.9 to 6 μ.

Example 17

5.85 g of 4-cyanatodiphenyl are dissolved in 50 ml of carbon tetrachloride and 2 ml of triethylamine are added. 3.86 g of 3-chlorophenol in solid form are then added in portions. A temperature increase of up to about 30 ^° C. occurs. The carbon tetrachloride and the triethylamine are drawn off from the clear, bright yellow solution. A yellow, thick oil remains, which soon crystallizes through. Raw f. 68 ⁰ C. Yield of O- (3-Clu ^ henyr) -O '- (diphenyl - 4) - imidocarbonic acid - bis - ester: almost quantitative. IR spectrum: strong band at 5.9 to 6 μ.

Example 18

To a solution of 4.5 g of 2-methoxyphenyl cyanate in 10 ml of diethyl ether are simultaneously 3.85 g of 4-chk ^ henol, dissolved in 10 ml of diethyl ether,

IO

and 4.35 ml of triethylamine were added with thorough stirring. Heating up to about 30 ^° C. occurs. After the ether and amine have been removed in vacuo, the O- (2-methoxyphenyl> O '- (4-chlorophenyl) -imidocarbonic acid bis-ester remains as a pale, thick oil. Yield: 7 g (= 84% of theory); IR -Spectrum: Strong band at 5.9 to 6 μ.

Example 19

At the same time, 3.6 g are added to a solution of 5.8 g of 2,6-diethylphenyl cyanate in 10 ml of light gasoline p-cresol, dissolved in light gasoline, and 3.4 ml of triethylamine poured in. Slight warming occurs on. Light gasoline and amine are stripped off in vacuo. What remains is the O- (2,6-diethyIphenyl) -O '- (4-methylphenyl) -imidocarbonic acid-bis-ester back as a light oil. IR spectrum: strong band at 5.9 to 6 μ.

Example 20

1.4 g of phenol, dissolved in ethanol, and 1.5 g of triethylamine are simultaneously poured into a solution of 2.6 g of 2,6-diethylphenyl cyanate in 10 ml of ethanol. The temperature rises to about 30 ⁰ C. Ethanol and amine are stripped off in vacuo, the O- (2,6-diethylphenyl) -O '- (phenyl) -imidocarbonic acid-bis-ester remains as a clear oil. Yield: 88% of theory. IR spectrum: strong band at 5.9 to 6 μ.

Example 21

An experiment carried out analogously to Example 20 with benzene instead of ethanol as the solvent resulted to a product identical in the IR spectrum. Yield: 86% of theory.

Claims (7)

Patent claims: 1. Process for the preparation of asymmetrical imidocarbonic acid bis-esters of the general formula 'R-O O - \ - R ' NH wherein R and R 'are aromatic or heterocyclic radicals different from one another and χ is an integer from 1 to 6, characterized in that an aromatic or heterocyclic cyanic acid ester is reacted with an aromatic or heterocyclic hydroxyl compound in the presence of a base. 2. The method according to claim 1, characterized in that the hydroxyl compound as Phenolate is used. 3. The method according to claim 1 and 2, characterized in that the reaction in one liquid medium is carried out. 4. The method according to claim 1 to 3, characterized in that the reaction is carried out at temperatures between 0 and 50 ^0C . 5. The method according to claim 1, characterized in that the reaction is in the presence from 0.01 to 1 mole of the base based on 1 mole of cyanate ester group. 6. The method according to claim 1, characterized in that the base is sodium hydroxide is used. 7. The method according to claim 1, characterized in that triethylamine is used as the base will.