DE1068263B - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

kl. 12 p 10

INTERNAT. EX. C 07 d

PATENT OFFICE

EXPLAINING PAPER 1 068 263

F 25847 IVb / 12p

REGISTRATION DATE: MAY 29, 1958

NOTICE:, i THE REGISTRATION AND ISSUE OF THE

Λ CJS LEGE S CHRI FT: NOVEMBER 5, 1959

3-Substituted 2,4-dioxo-tetrahydroquinazolines have already been described in isolated cases in the literature. So get the corresponding 3-aryl-substituted 2,4-dioxo-tetrahydroquinazolines are obtained from anthranilic acid and aryl ureas (Ber. German former Ges., 38, 1212 [1905]). The yields are low in this process and are 20 to 25%. 3-MethyI-2,4-dioxo-tetrahydroquinazoline can be obtained from anthranuic acid-N-methylamide and urea can be produced in the melt at 180 to 200 ° C. (Journ. Prakt. Chem., 39, 147 [1889]). Yields are not given. However, the reaction products contain larger amounts of impurities and have to be cleaned by repeated recrystallization with high losses. Furthermore, the production of 3-Aryl-2,4-dioxo-tetrahydroquinazolines from aromatic primary monoamines and carbon dioxide at temperatures above 175 ° C and pressures above 3300 atmospheres known (U.S. Patent 2,680,741). The yields are between 20 and 70%. Because of the extreme reaction conditions, this process is not technical Interest.

It has now been found that 2,4-dioxo-tetrahydroquinazolines substituted in the 3-position can be obtained in good yield and a high degree of purity if O-sulfonyl compounds of N-oxyphthalimides are obtained general formula

Method of manufacture
of substituted in the 3-position
2,4-dioxo-tetrahydroquinazolines

Applicant:

Paint factories Bayer Aktiengesellschaft, Leverkusen-Bayerwerk

Dr. Engelbert Kühle, Cologne-Stanimheim,
and Dr. Richard Wegler, Leverkusen,
have been named as inventors

NO-SO ₉ -R

in which Z is an optionally ring-substituted and / or ring-hydrogenated benzene ring and R is an alkyl, aryl or Dialkylamino radical with compounds of the general formula

R'N H ₂

in which R ' _{denotes H, OH NH 2} or an organic radical, or reacts with carboxylic acid hydrazides or sulfonic acid hydrazides.

In the case of an O-sulfonyl compound of N-oxyphthalimide, the course of the reaction can be as follows Reaction scheme are given:

CO,

CO '

NOSO ₉ R + 2 R'NH,

, NH.

XO

CO
NO'

+ RSO ₂ OH • R'NH ₂

Examples of compounds of the formula R'N H ₂ are such. B. tetrahydrofuran, dioxane or dimethyl

primary aliphatic, cycloaliphatic, aromatic or formamide.

heterocyclic amines or organic hydrazines, the reaction products obtained may contain a free amino group as an intermediate. 5 ° products can be used.

The new process is generally carried out in aqueous The O-sulfonyl compounds required as starting materials

Medium at room temperature or at elevated temperatures of the N-oxyphthalimide can be used in a simpler

temperature carried out. It is still possible to do it the way around and with good yields (up to 85%)

to be carried out in organic solvents, phthaloximes and corresponding sulfochlorides are

909 647/409

Claims (1)

(see, for example, German patent specification H3 050). example 1 In IOOml of a 10 ⁰ / "strength hydrazine hydrate carries a nan in portions with stirring 12 g of finely powdered TF (methanesulfonyloxy) phthalimide. A violent reaction occurs immediately, with the temperature rising to around 50 ° C. It is stirred for a short time after and sucks las formed 3-amino-2,4-ib dioxotetrahydrochinazolinkalt F. 296-297 ° C. Yield: 6.9 g = 78 ° / ₀ of theory. The following connections are established accordingly: / NH _x Amine I.
-NO' Fp: yield R '= ⁰ C 7o ammonia -H 352 90 Hydroxylammary -OH 322 to 326 75 Methylamine - -CH _s 240 to 242 quantitatively Amino vinegar -CH ₂ COOH 298 77 acid (as Sodium salt) Aminoethanol - -CH ₂ CH ₂ OH 257 80 Example 2 34 g of isonicotinic acid hydrazide are dissolved in 200 ml of hot water and 30 g of N- (methanesulfonyloxy) phthalimide are added while hot. The mixture is stirred for 1 hour at 90 ° C., filtered off with suction while cold and the product is rewashed with acetone. 32 g (= 92% of theory) of 3-isonicotinoylamido-2,4-dioxo-tetrahydroquinazoline of melting point 309 to 310 ^° C. are obtained The 3-picolinoylamido compound with a melting point of 290 ° C. is obtained accordingly when picolinic acid hydrazide is used. Example 3 A mixture of 34.4 g of benzenesulfohydrazide and 20 g of N- (MethanesuliQnyloxy) -phthalimide is dissolved in 200 ml of water Heated on the steam bath for 1 hour; the resulting reaction product is sucked cold and with acetone rewashed. 18 g = 69% of theory of 3-benzenesulfonamido-2,4-dioxotetrahydroquinazoün, mp. 277 ° C PATENT CLAIM: Process for the preparation of 2,4-dioxo-tetrahydroquinazoene substituted in the 3-position, thereby characterized in that one uses O-sulfonyl compounds of N-oxyphthalimides of the general formula II ao _c Z NO-SO ₂ -R II ο in Z an optionally ring-substituted and / or ring-hydrogenated benzene ring and R a Means alkyl, aryl or dialkylamino radical, with compounds of the general formula R ^f NH ₂ in which R ' _{denotes H, OH 1} NH ₂ or an organic radical, or reacts with carboxylic acid hydrazides or sulfonic acid hydrazides. Considered publications:
U.S. Patent No. 2,680,741.