DE80568C - - Google Patents

Description

IMPERIAL

PATENT OFFICE. Y%.

CLASS 12:

mix apparatus and processes.

Dr. Ernst Täuber in Berlin.

Ethenyldiphenylamidine.

Patented in the German Empire on July 20, 1894. Longest duration: March 15, 190g.

The methods described in parent patent no. 79868 for the preparation of Ethenyl-ρ-diethoxydiphenylamidine can also be used to add to a number of other to reach as yet unknown amidines, which can be used as medicinal products.

The following amidines have been presented: ι. Ethenyl-p-methoxydiphenylamidine,

2. Ethenyl-p-ethoxydiphenylamidine,

3. Ethenyl-p-ethoxy-p-oxydiphenylamidine,

4. Ethenyl - ο - methoxy-o-methoxydiphenylamidine,

5. ethenyl - _{ο-methoxy-p-methoxydiphenylamidin:}

6 .. ethenyl - ρ - methoxy-p-methoxydiphenylamidine,

7. Ethenyl-o-ethoxy-ρ-methoxydiphenylamidine,

■ 8. Ethenyl-o-methoxy- ο-ethoxy diphenylamidine,

9; Ethenyl - ο - äth oxy - ο - äthoxydiphenylamidin, <

10. Ethenyl-o-methoxy-p-ethoxydiphenylamidine,

11. Ethenyl - ρ - methoxy-p - ethoxydiphenylamidine,

12. Ethenyl - ο - ethoxy-p-ethoxydiphenylamidine.

The * representation of these amidines is done according to that described in the main patent Method by instead of p-phenetidine here p-amidophenol respectively. ο-anisidine or p-anisidine or o-phenetidine or finally a mixture of two of these amines; or by replacing phenacetin with the acetone compound of one of the amines mentioned respectively brings a mixture of two acetal compounds into use. Not all methods deliver equally good results in every single case. So it is recommended for the representation those amidines which have two different radicals, e.g. B. the aniline residue, the p-phenetidine residue on the other hand contain to choose the method according to which an acetone compound with a hydrochloric acid salt is heated for a long time. If, on the other hand, the method is used, after which is a mixture of molecular quantities of the two amines with glacial acetic acid and phosphorus trichloride is heated, one obtains the asymmetrical amidine with the two symmetrical ones Amidines are contaminated and the three products must first be separated by crystallization the base mixture or the salts.

The illustration of the amidines to be protected by patents is given by the following examples explained:

Example!:
Ethenyl-p-methoxy-p-methoxydi-

phenylamidine.
4 weight th. p-anisidine and 1 th. glacial acetic acid

are mixed. The cooled mixture is crushed and with good cooling with 2 weight th. Phosphorus trichloride gradually added. Mix as much as possible while allowing the mass to warm up slowly by removing the cooling water, heat, after the voluntary heating has ceased, for a few hours in an oil bath to about 160 ° and then let it cool. The product is then heated with water and excess alkali, whereby a thick mixture of bases - amidine and anisidine - is deposited. After cooling, it is filtered and the crude product remaining on the filter is crystallized from about 60 per cent. Fuel to; it is almost _pure: get Ämidin. It is obtained in a state of complete purity by recrystallization from benzene-ligroine.

Example II:

Ethenyl - ρ - methoxy - ρ - ethoxydiphenylamidine '.

18 weight th. finely grinded phenacetin with 30 weight th. Benzene poured over it and with cooling 10.5 th. phosphorus pentachloride (or 15.3 th. phosphorus oxychloride or 14 th. phosphorus trichloride) added. Immediately add to the mixture while cooling a solution of 12.5 th. p-anisidine in 20 th. benzene and shake well. The reaction is brought to an end by heating for several hours, the benzene is distilled off, the resinous, pale yellow residue was taken up with hot water and the ethenyl base precipitated from solution with ammonia. The cleaning is carried out as in Example I.

Example III:

Ethenyl - ρ - ethoxy - ρ - oxydiphenylamidine.

15 weight th. Acet-p-amidophenol will be with 50 weight th. Poured over benzene and while cooling 1.5.5 weight th. Phosphorus oxychloride added. For this purpose, 14 Th. P-Phenetidine in 20 Th. Dissolved benzene given. By slowly warming up in the water bath until complete When the benzene is driven away, the reaction is brought to an end. Then the residue with Absorbed water and a small amount of regenerated amidophenol at first carefully Addition of soda precipitated. The ethenyl base in the filtrate is then replaced by excess Like soda in the warmth. The resinous base deposited in this process is diluted in Dissolved potassium hydroxide solution, shaken the solution out with ether to remove small amounts of p-phenetidine and the pure ethenyl base finally precipitated from the aqueous alkaline solution by means of carbonic acid. The base falls resinously off, is melted into a lump by heating and then by cooling froze. The aqueous salt solution is poured off and the base with washed in cold water. By dissolving in dilute hydrochloric acid and vigorous evaporation the hydrochloric acid salt is obtained as a crystalline, white mass.

Example IV:

Ethenyl-o-ethoxy-p-ethoxydiphenyl-

amidine.

Equal parts by weight of phenacetin and hydrochloric acid o-phenetidine are rubbed together and heated the mixture in an oil bath at 180 ° for 15 hours. The product that Dark colored and thin when heated, boil with 20 times the amount of water. Then it is allowed to cool, and the solution is filtered from a little resin and something unchanged Phenacetin and the new base precipitates in the filtrate due to alkali. The raw base is cleaned as above.

Example V:

Ethenyl-ο-methoxy-p-ethoxy diphenylamidine.

A mixture of 16.5 weight th. Acet-oanisidin and 18 weight th. Phenacetin is spread in a thin layer and heated to approximately 150 ⁰ and for several hours, a slow stream of dry hydrochloric acid gas passed over it. The reaction mixture is dissolved in hot water, ammonia is added to the filtered solution, and the precipitated crude base is then recrystallized from aqueous alcohol until the melting point is constant.

Example VI:

Ethenyl-o-ethoxy-p-methoxydi-

phenylamidine.

An intimate mixture of 16 weight th. hydrochloric acid ρ - anisidine and 17.5 weight th. Hydrochloric acid ο-phenetidine is heated ^{to 230 to 240 0 for} 2 hours with 6.6 th. acetonitrile in a closed vessel. The dark Reactionsgemisch is contacted with water in ^ι possible "solution, precipitated from the filtered solution the amidine base with alkali and the product of fuel recrystallized has become constant until the melting point.

Example VII:

Ethenyl-p- methoxy-p- methoxydi-

phenylamidine.

2 weight th. Acet - ρ - anisidine and 1 weight th. Phosphorus pentasulphide are combined

grated and in a spacious vessel heated to 100 to 120 °. Then you add slowly io weight th. Add alcohol, with strong evolution of hydrogen sulfide. After this has ended, it is filtered and the filtrate is treated with sodium hydroxide solution and twice the volume of water. The resulting deposit is after some Hours filtered off and by dissolving in hot, very dilute hydrochloric acid, reprecipitation with Ammonia and recrystallization from 60 per cent. Fuel cleaned.

Example VIII:

Ethenyl- ρ - methoxy -p - methoxydiphenylamidine.

Phosgene gas is passed over molten p-anisole glycine-p-anisidide heated to 140 to 150 ^{0 for a few hours.} The reaction mixture is brought into solution as far as possible by very dilute hot hydrochloric acid, undissolved resinous substances are filtered off, and the crude amidine in the filtrate is precipitated with alkali. It is cleaned as described.

Tabular overview of the properties of the new amidines.

No. Surname Crystal shape,
M.p. solubility Hydrochloride sulfate I. Ethenyl -ρ - methoxydiphenyl-
amidine viscous OeI;
M.p.
295 to 300 °
at 80 mm easily soluble
in alcohol and
Ether;
poorly soluble
in petroleum ether
and H ₂ O easily soluble easily soluble 2. Ethenyl - ρ - ethoxydiphenyl-
amidine . 85 ⁰ C. easily soluble
in alcohol and
Ether;
poorly soluble
in petroleum ether
and H ₂ O easily soluble easily soluble 3 · Ethenyl - ρ - oxy - ρ - ethoxydi-
phenylamidine semi-solid easily soluble
in alcohol;
poorly soluble
in H ₂ O easily soluble 4 · Ethenyl-0-methoxy-0-meth
oxy diphenylamidine Needles;
99 ⁰ C easily soluble
in ether;
easily soluble
in alcohol;
poorly soluble
in H ₂ O very easy sol
Lich in H ₂ O easily soluble S- Ethenyl - 0 - methoxy-p - meth-
'oxydiphenylamide m . Prisms and
Needles;
108 ⁰ C. easily soluble
in alcohol and
Ether;
poorly soluble
in H ₂ O very easy sol
lich;
crystallizes out
very cone. Lo
sings
(Warts) very easy
soluble 6th Ethenyl-p-dimethoxydiphenyl-
amidine 105 ⁰ C. easily soluble
in alcohol and
Ether;
difficult in
Petroleum ether and
H ₂ O easily soluble easily soluble 7 · Ethenyl-o-ethoxy-p-methoxy-
diphenylarmdin Warts;
85 ⁰ C. easily soluble
in alcohol and
Ether;
difficult in
Ligroin extremely light
soluble very easy
soluble 8th. Ethenyl-o-methoxy-o-ethoxy-
diphenylamidine semi-solid easily soluble
in alcohol and
Ether extremely light
soluble very easy
soluble;
poorly soluble
in H ₂ S oil
containing H ₂ O

No. Surname Crystal shape,
M.p. solubility Hydrochloric! , .Sulphate δ Ethenyl - ο - diethoxydiphenyl-
amidine . semi-solid easily soluble
in alcohol and
Ether easily soluble;
crystallizes out
cone. solution
(Warts) very easy
soluble;
poorly soluble
in H ₂ SO ₁ -
hold ί? ₂ Ο ι ο. Ethenyl-o-methoxy-p-ethoxy-
diphenylamidine Prisms and
Needles;
107 ⁰ C. easily soluble
in alcohol and
Ether extremely light
soluble very easy'
soluble ^: II. Ethenyl-p-methoxy-p-ethoxy-
diphenylamidine 98 ⁰ C. easily soluble
in alcohol and
Ether;
poorly soluble
in petroleum ether
and H ₂ O hygroscopic easily soluble. 12th Ethenyl-o-ethoxy-p-ethoxydi-
phenylamidine Warts;
75 ⁰ C easily soluble
in alcohol and
Ether;
difficult in
Ligroin easily soluble very easy
soluble.

Claims (4)

Patent claim: Procedure for displaying the following new Ethenylamidine: Ethenyl-p-methoxydiphenylamidine , Ethenyl - ρ - ethoxydiphenylamidine, ethenyl - ρ - ethoxy - ρ - oxydiphenylamidine, Ethenyl-o-methoxy-o-methoxydiphenylamidine, -Aethenyl-o-methoxy-p-methoxydiphenylamidine, Ethenyl-p-methoxy-p-methoxydiphenylamidine, Ethenyl - ο - ethoxy - ρ - methoxydiphenylamidine, ethenyl - ο - methoxy - ο - ethoxydiphenylamidine, Ethenyl - o- ethoxy - ο - ethoxydiphenylamidine, ethenyl - ο - methoxy - ρ - ethoxydiphenylamidine, Ethenyl - ρ - methoxy - ρ - ethoxydiphenylamidine, ethenyl - ο - ethoxy - ρ - ethoxydiphenylamidine, consisting in the fact that in the process of main patent no. 79868: i. the p-phenetidine replaced by one of the following bases: o-anisidine, p-anisidine, o-phenetidine, or by a mixture of: p-anisidine and aniline, p-phenetidine and aniline, p-phenetidine and p-amidophenol, o-anisidine and p-anisidine, o-phenetidine and p-anisidine, o-anisidine and o-phenetidine, o-anisidine and p-phenetidine, p-anisidine and p-phenetidine, o-phenetidine and p-phenetidine; 2. Phenacetin replaced by the acetone compounds, which differ from those in claim 1. named bases respectively. Derive base mixtures; 3. the thiophenacetin replaced by the thibacet compounds, which differ from the bases mentioned in claim 1. BEZW. Base mixtures derive; 4. replaces p-phenetolglycine-p-phenetidide through the raw products of the influence of. Chloroacetyl chloride and bromoacetyl bromide to an excess (more than 4 mol.) of the bases mentioned in claim 1 and Base mix.