DEP0044595DA - Process for the preparation of nitrogenous thioethers - Google Patents

Description

Dr. Clemens Lutter (Wuppertal) Dr. Srnst Cauer (Leverkusen)

Kn / Beauty Leverkusen, 27 May 1949

"Process for the manufacture of thioethurine

By the action of cyanides for connections _s as they arise from formaldehyde ~ bisulfite and amines, be = deprived borrowed Aminoaäurenitrile erbalten "The implementation of such Fortnaldehyd-Bisulf itverbindungen of amines with other salts as cyanides has not yet been disclosed"

It has now made the surprising observation that τοη using alkali metal sulphides can be easily replaced instead of the cyanides of Sulfitrest in Amlnoformaldehyd-bisulfites * to sulfur "This converts into good goal for untex ^a meeting of sweier molecules corresponding to the following match thioethers:

R.
O ₈ SO ₀ Ia + ISoS ° -X N-CH ₉ -S-CH ₀ -H + 2Ia ₀ SO-

R ⁰ E

The sugrunde lying amines can be substituted in any way o Particularly suitable for the implementation are the formaldehyde = -Bisulfitver = »

Windings "When using primary amines, the exchange also takes place, but the sulfur ethers obtained in this way cannot be cleaned because of their ease of substitution"

The new compounds are mostly oily _s share kristal = lisiert and are suitable as fulkanisationebeschleuniger and as Ewieehenprodukte for the production of dyes and pharmaceuticals "

1188 g technical HatriunibiBulfitlösung (4 moles IaHSO ₅ containing) with cooling with 400 g of 30 $ strength Pormaldehydlösung and then with! 54O _8, 8 g 52 _s reacted for 8 $ strength Dimethylaninlösung ₀ To the reaction mixture is added a warm solution of 480 g Batriuraaulfid in Given 100 ecm of water and then heated to 50 ° for 1 hour. After cooling, the precipitated inorganic substances are suctioned off and the oil removed from the piltrate is extracted repeatedly with ether after saturation with potassium carbonate. Ether and oil are combined and dried with potassium carbonate. After evaporation of the ether, a light yellow, smelling smelling oil remains, which can be purified by distilling small amounts in a vacuum. _C. Kp «^ Q _{m &} . 69 ° with little decomposition,

297 g of 35% sodium bisulfite solution are first mixed with 100 g of 30% formaldehyde solution and then with 99 g of hexa-

metbylenimine reacted. After addition of 120 g of sodium sulfide _g dissolved in 50 cc Wasaery and stirring for one hour is saturated with potassium carbonate and suegeäthert * The dried with potassium carbonate ethereal solution leaves after evaporation of the ether, a "basic smelling colorless oil ₈ that could not be further purified as such . the liehst by evaporating a solution of the crude product in dilute hydrochloric acid at mög <= low temperature is obtained Yakuum and Umlö "oen of ethanol purified Bihydroehlorid provides white Kristal!" Ie aear ₉ at 188 - 189 ° melt "

A teehni sulphite liquor containing 104 g of sodium biaulphite is first reacted with 100 g of 30% formaldehyde solution and then with 85 g of piperidine. To this, a Nie = "mixture containing Derschlag a solution of 120 g of N © ~ triumsulfid in 50 cc of water and ο stirred for 1 hour The resulting gray precipitate is filtered off with fesser washed ₉ cleaned dried and purified by reprecipitation from Leichtbensin" are Bs white cadre obtained, which schiaelsen with previous sintering at 48 «,

Example 4 s

149 g of 55% sodium sulfite solution are mixed with 50 g of 30% formaldehyde solution and then with 43.5 g of morpholine as normally implemented. To the mixture containing a precipitate, 60 g of hatriucia sulfide, dissolved in 25 com Waoser, are added

After stirring for an hour, it is suctioned off and the inorganic residue is washed with water. When the filtrate is saturated, it is increased Potassium carbonate separates the new compound in the form of white crystals <, After suction they are converted from acetone * “White crystals from the F ^. 104 °.

Example 5 j.

297 g of 35 ^ strength latriutnbisulfitlo'sung be umgesetst with 100 g of 30 $ strength Formaldehydlc'sung with 71 B Pyroll'idin. After adding 120 g of hydrous sodium sulfide dissolved in 30 ecm of water, the mixture is stirred for 1 hour and then cooled with biscuit. After the precipitate has been suctioned off, the filtrate is saturated with potash and the precipitate that occurs again is combined with the first obtained. The precipitations are absorbed in ether. The filtered ether solution is dried with Kaliuffloarbonat and the remaining after evaporation of the ether residue is recrystallized from petroleum ether ₀ tfeifle crystals of mp 35 ° _0.

297 g of 35% sodium bisulfite solution are reacted with 100 g of 30% formaldehyde solution and 59 g of n-propylamine. After the addition of 120 g of crystallized sodium sulphide, dissolved in 50 ecm of water, an oil separates and is separated off. The aqueous portion is united after saturation with potash several times ausgeätherto ethereal solution and oil - <- / Eo-t-bag dried ₀ After evaporation of the ether remains behind a pale yellow, sulfur-containing oil "the kennte be cleaned nioht ₀

Claims (1)

Pa_-t en tans Bruo h t Process for the production of thloethers, characterized in that alkali stilfide is brought into effect on the coneensation products obtainable from amines and formaldehyde bisulphite. Bel splice 7 i, 21 g Porraaldehyd-NEtriurabisulfit ^ VerMndttng das l «imino = 4 = m @thylbensol are in 200 com. Dissolved water and added 24 g of sodium sulfide in 50 oom water to the solution. The rapidly precipitate is filtered off with suction after standing for several hours, and washed * by dissolving in a little ether and addition of petroleum ether obtained color loss crystals. That at? 2 ° zn a turbid liquid melt ₀ Example. 8th;_ 26 g of formaldehyde sodium sulfide compound of the amino-2-chloro-5-methylbenzene are dissolved in 200 com of water at 60 ° and a solution of 24 g of sodium sulfide in 50 ecm of water is added . The compound, which immediately solidifies as a tendon, is sucked off after standing for several hours and can be purified by dissolving it from ether with the addition of petroleum ether. Colorless Crystals Pjf. 114 - 115 ° o In the same way the following are obtained from the formaldehyde-hyd-sodium bisulfite compounds: l ~ Amino ~ 4 ~ chlorobenzene is an amino thioether from FW ₀ 96 ° ₉ colorless crystals from methanol l-Amino-2 _s 4 = dishlorbensols an aminothioether from F ^ ₀ 81-82 ⁰ J colorless crystals from methanol l = amino = 4 "» nitrobenzoic an aminothioether of fio 208 ° yellow © crystals of a lot of aeeton, l = aaiino-4-raethoxyb @ n2olgi an aainothioether of m.p. 85-86 ^c Farfelless crystals from aeeton and ether Aminobenzene-4- ° carboxylic acid- an aminothioether of F ^, 148 ° colorless crystals from aeeton -Aminonaphthalene an aminothioether from S ^. 118 °, Acetone and alcohol crystals, Example ._, 9.s. I50 g Hatriuinbisulfitlösimg be such given by 120 g ilatriumsulfid in little? '' Ater with 50 g of 50 tigern formaldehyde and reacted 54 g of benzylamine "by adding 100 cc of water and gently warming the separated crystals in solution placed Zn the clear solution is . The oil which precipitates out immediately is taken up after standing for several hours in Athey. After the ether, which has been washed with water and dried over sodium sulphate, has evaporated, a viscous oil flashes behind, from which crystals separate when standing. Adhering oil freed and redissolved after suction from boiling methyl alcohol. Colorless needles F /, 94 °. By replacing the benzylamine 61 g N = Methylbensylamin, then on addition of Sulfidlb'sung also an oil erhalten- After standing for some time, the reaction mixture is «asked for a short time in ice, this solidified the oil into crystals ,, the aspirated with _s T / 5o can be washed and uragelissol'st from methyl alcohol. Colorless Crystals P ^ ' _o 58-