DE1593951A1 - Process for the preparation of 2-chloroethanesulfonic acid salts of organic nitrogen bases - Google Patents

Description

DR. ING. F. WUBSTHOFF DIPL. ING. G. PUI-S «I C Γ» Ο Π C DR.B.T.PBOHMANN. imbfo »83 06 51 | θ3θϊίθ I PATENTANWÄLTE ^^^ «x '^ kO« »

U-32 831 description

to the patent application
Produits Chimique PECHINEY-SAIM-GOBAIIi 16, Avenue Matignon, Paris (8e) / France

concerning

Process for the production of 2-chloroethanesulfonic acid salts of organic nitrogen bases

The present invention relates to a process for the preparation of new salts of organic nitrogen bases, on the one hand from the anion of 2-chloroethanesulfonic acid ClGHp-GHpSO "^ and on the other hand from the Compose cation of an organic nitrogen base by reacting 2-chloroethanesulfonic acid with organic f see nitrogen bases.

The implementation according to the invention is effected in a simple manner by mixing the reaction partners, wherein the amount of organic nitrogen base used is at least one equivalent of base per mole of 2-chloroethanesulfonic acid is equivalent to.

009834/1984

• The formation reaction of the 2-chloroethanesulphonic acid salts of the nitrogen bases proceeds as an addition reaction according to the equation

J-CH ₂ -SOoH + organic nitrogen base / "ClGH ₉ -GH ₉ -SUo 7" / "H-organic nitrogen base 7 ⁺

ι - ■ '■ - "

or as a condensation reaction with elimination of water or hydrohalic acid according to the following reaction equations:. ■

-GH ₂ -SQoH + quaternary ammonium hydroxide -} H ₂ O + / "GlGH ₂ -GH ₂ SOo 7« ^ fquaternary ammonium ^ -CH ₂ -SGoH + quaternary es- ammonium shark ogenide

> Hydrogen halide. + / "Gl GH ₂ -GH ₂ -SO" 7 | 7 quaternary es

ammonium

The implementation is made possible by using pure 2-chloroethanesulphonic acid as the starting material, the production of which in the pure state is described in another application.

Those suitable for the process according to the invention organic nitrogen bases are the primary, secondary or tertiary aliphatic, alicyclic and aromatic Amines, as well as heterocycles x ^ ie pyridine, quinoline, Pyrrolidine, pyrroline, pyrrole, morpholine, pyrrolidone,

_ ■ 3 -

009834/198 V

Pyrimidine, piperidine, pyrazine, piperazine and the triazoles and triazines.

According to a special embodiment of the invention Process are the organic nitrogen bases and the 2 ^ chloroethanesulfonic acid in stoichiometric ff closely implemented with each other. Stoichiometric ■ "means -that 1 mole of acid has a basic nitrogen function used xiird, - .., - ■ «-. . '

The reaction according to the invention is preferably used for 'Formation of salts of organic nitrogen bases in counter- ■' was a suitable solvent such as methanol, Ethanol, ether and / or dioxaii made.

In general, the reaction parts are mixed with one another at low temperature, since the reaction takes place almost immediately with a very low yield. ■ ■ g

. The. Implementation: runs slightly exothermic; it can therefore It may be advantageous to cool the heat exchanger.

The essential salts of the organic nitrogen bases are / ranz generally - as starting materials for syntheses, preferably used as a propellant. ■;

The invention: becomes anhanc. r; he following examples ii-iher explained. .... '-

.009834 / 1984

example 1

Reaction of methylamine with 2-GhIoräthan sulfonic acid .;

Methylamine was passed into an ethereal solution of 2-GhIoräthansulfonsäure with 10 parts by weight of acid to 50 parts by weight of solvent until the formation of a precipitate ceased. The precipitate was filtered off and recrystallized from methanol in the form of white platelets of Pp 135 G. The yield before recrystallization was 95 %, after recrystallization 76%,

Elemental analysis of ClCHgCHgSO "- /" H-NH ₂ -CH "_7 ⁺

GH Gl N Found ■ 20.5 5.7 20.3 7.75

Calculated for C ₃ H ₁₀ SO ₃ NCl 20.5 5.7 20.2 7.95

Example 2 ■

Implementation of isopropylamine with 2-chloroethanesulphonic acid. -. -. "■

1 mole of isopropylamine was dissolved in ether in 5 times its weight and added to the solution of 1 mole 2 - <? Chloroethanesulfonic acid given in 5 times its weight in ether. The precipitated precipitate was filtered off, collected and recrystallized from methanol.

- 5th

009834 / 198'4

The connection was in the form of white platelets obtained from Fp Ι3ό G. ■ "/■. ".--

The molecular weight was titrated by neutralization with Soda determines, and corresponds to the salt.

HNH ₂ -GH

Found . 193
Calculates 203.5

Example 3

a) Two iither solutions containing 2 mol. 2-chloroethanesulfonic acid or 1 mole of ethylenediamine contained mixed together. The crystalline '

white precipitate (yield 87 %) was filtered off and washed with ether. The bis-2-ehlorethanesulfonate of ethylenediammonium melted at 314 G.

G HO N Gl S

Found 20.7 5 '27.4 8.4 19.8 18.3

Calculated-for _9n , • "■■ £ _1O ^ _L , o η _{Λ9 9n} ^ _1P " _A

0, H ₁ OUxN ₀ Gl ₀ S ₀ ^2O > ^{63 5} ^ ^{19 2? '48 8} ' ^{02 20} » ^{3 18 '36}

BAD O?! [Q | js ( _A i

009834/1964

• Td) The experiment was repeated with the modification that only 1 mole of acid was mixed with 1 mole of diamine. The resulting mixture contained approximately 66% mono-Äthylendiammonium chloräthansulfonat 2 and about 34 $ iithylendiammonium-bis-2-chloräthansulfonat.

Example 4. ....-.-. ■ "-

a) Under the same conditions as in Example 3 were 2 hol 2-Chloräthansul.fonsäure with 1 mol of hexamethylene amine mixed. A crystallized white product was obtained in "a" yield "of" 90% > ä obtained ", the hexamethylenediammonium bis ~ 2-chloroethane sulfonate. at the front mp -2-29 ° C.

G H 0. N. Gl S Found . 29.9 6.3. 24.4 7.1 17.3 15.7

Calculated for _{on rc uc o} " , / ,, _Λη ,," _Λ , _{Ο (} ,

G _1n H., 0, N ₉ Gl ₉ S ₉ ²⁹ ' ^D ö, 4b 23, ö 6.9 17.49 Ib * U

IU CO OCCC

b) If only 1 mole of acid was mixed with 1 mole of diamine, the resulting mixture contained about 80 γό hexa-. methylenediammonium bis-2-chloroethanesulfonate and about 20 % hexamethylenediammonium mono-2-chloroethanesulfonate.

Examples 5 to 12

They were as described in Example 2 Method of working further primary amines with 2-chloroethane

ba ORIGINAL

009834/1984

IA-32-831

sulfonic acid implemented. The -! Results' are in the Table I summarized below. As a solvent was in Examples 5 to 11 iither and in Example 12 Methanol -Used.

Table I.

At-. Organic chloroethanol sulfonate's

play nitrogen- nitrogen base _, appearance and base / "GlGH GKgSO ^ Z'fH-nitrogen base / physical

xlatton

Gross formula

Constants

$ ■■ n-Butylamine ΝΗ «- (ΟΗ.,.)« - ΟΙίο Gr

J ¹ y J O

J "

«ΟΙίο Gr

J · J O

Allylamine KH ₃ -CHp-GH = CH ₂

aniline

white plates umkr. from G
Mp 113

white plates umkr. from CHoüH Pp 97Og

white Hadelη rec. the end

Fp ^J l98 ⁰ G.

ro sa Hadeln umkr. from GHoüH _ Fp ^J l95 C

9834/198 BAD GRIGLNAL

Table I (continued)

Inorganic Ghloräthanolsulfonat der

play nitrogen-nitrogen base, appearance and

base / "GlCH ₂ CH ₂ SOo T /" H-nitrogen base 7 physical cation ^ "~ gross formula" constant

• 9 Cyclohexyl- ⁺ NH ^ - C ₈ H ₁₈ O ₁ NClS white plat-

amin I ^J ^ chen umkr.

from GHoOH Fp 165 ^Ö G

Dodecylamine NHoC ₁₂ H ₂₁ - G ₁ ^ Ho ₂ O ₃ NClS white platelets ■ - ^ JJ chen umkr,

from CHopH, mp 10 ° C

Stearylamine ^ HoC.nH ^ C _O A ^ ^Ü 3 ^WG1S white plat--

j Io ^{3/20 J} chen umkr. the end

GHoOH

109 ° C

Monoethanol- NH ₃ C ₂ H ₁ I ₊ OH C ^ H ₁₂ O ^ NG1S white platelets

^am i- ⁿ umkr. the end

M.p. ^J 63 ° G

Examples 13 to 19 ".

According to the procedure given in Example 2 xmrden aliphatic, alicyclic and heterocyclic secondary amines reacted with 2-chloroethanesulf'onic acid. The solvent used in Example I3 was ethanol, in the

Athlete
Examples 1h to 18 / and in Example 19 methanol

009834/198 4 bad ö ^ ginäi

turns. The results are shown in Table II below summarized. . .

Table II.

at- organic chloroethanol sulfonate

play nitrogen _ nitrogen base '., appearance and

base / GIGH ₂ GHqSOo 7 "/ ~ H-nitrogen base 7 physical

Cation ^J "~ gross formula" constant

Dimethylamine

HH ₉

yellow oil cannot be distilled |

4 ° = 1.4718

IM- dibutylamine

Turn over white plates *.

-f.
Morpholine NHV

white plates umkr. from GHoOH · Pp 92 ^J C

Piperidine

GH ₂ _ CH ₂

GH, GH ₂

brown oil cannot be distilled ΐ ^Ί ρ 9 ° G

- 10 -

009834/1984

^bath

. ίο-

iA-32

_Ί 593951

Table II (continued)

Inorganic GhIoräthanolsulfonat der

play nitrogen- "'nitrogen base ₊ appearance and

'"- ■■■" base ■ / "GlGH ₂ GFi ₂ J-SiI _- /'"/~ES.ticksto;ff'base_7 -physical

Cation - ^ ". '.' Gross formula ~ constants

Pyrrolidine

GH

2 \. ^: GH \ 2 υπ, -,

C, H ₁ ^ ο j.

brown oil do not distill

Pyrroliaon

GH

¹ ^

= O

C _n H ₁₉ OJSfGlS

not or distillable sc

oil

η ^u = 1.4903

Diethanoiamine

xG

--r

'JM ₁ --Ü ^ J-IGlS--'

the same oil cannot be distilled

For example, 2 0 to 2?

• In the following table III the results of the

Try . in · '

together with the amount according to example 2 2-GhIoräthansulfonsäure and an aliphatic, aromatic or this is a heterocyclic tertiary amine. or a quaternary it. Ammonium hydroxide were reacted with each other. The implementation was in the examples 20 to 25 in ether and in Examples 26 and 2? made in methanol.

0 09834/1984

- 11 -

bad original

IA-32

Table III

Inorganic
play nitrogen
• "base

GhIorethanolsulfonat der Nitrogen base appearance and

ΛΗ-StictetoffbaseJ

20 trimethylaroin

NH GH

GH,

white plates umkr. from GH ₀ OH Pp ^Ö

21 triethylamine

G ₂ yellow oil cannot be distilled

n ^ ⁰ = 1, ^ 721

22 diethylaniline,

H ₁ ;

2 ^H 5

C ₁₂ H ₂₀ O ₃ NGiS yellow 01 cannot be distilled

n ^ °; = 1.5072

23, pyridine

vjeisse platelets umkr. from GH ^ OH m.p. 138 ⁰ G

2 if- Ghiholin

orange plates around it from CH “OH Pp 128 ° C

- 12 -

009834 / 198A

IA-32 8-31

example

organic nitrogen / -

Table III (continued)

GhIorethanolsulfonat der
Nitrogen base

Appearance and

Jn / "GlCH ₉ CH ₉ SOo 7" / "H-nitrogen base 7 physical ^se " cation ^J ~ "gross formula" constants

25 8-hydroxyquinoline

H OH 41

yellow needles umkr. from GH ₃ OH

Fp ⁰

26th

Triethanol- CH ₉ -GH ^ H

amine. S ² ^ -

NH-GH ₂ -GH ₂ -OH GH ₂ -CH ₂ -OH yellow oil not distillable

n ^ ° = 1, ^ 908

27 Tetramethylammoniurahydroxyd _n ",

ο tr

GH G ₆ H ₁₆ O ₃ NGlS

! Geisse platelets umkr, off

Claims

7223

009834/1984

BATH

Claims (7)

DR.B.v.PBOHMAriN TawFOir 32 06 81 Λ Γ Q O Q C PATENTANWÄLTE TILiaiim ADBBBSM ι '"" *' "'■■'. 1A-32 831 P a t e η t a η s p, r ü c he 1. Process for the production of 2-ehloräthaasulfon- · acidic salts of organic Sisicks-boff bases, characterized in that at least one equivalent Base per mole of 2-chloroethane sulfonic acid, if appropriate implemented in the presence of a solvent. 2 ο The method according to claim 1, characterized ge ke η η - is characterized in that 2-Ghloräthansulfonsäure converted, which has been obtained by hydrolysis of 2-Ohloräthansulfonylchlorid with alcohol or aqueous alcohol. . 3. The method according to claim 1 and 2, characterized in that the organic stick f substance base an aliphatic, primary, secondary or tertiary amine used. 4. The method naoh claim 1 and 2, characterized g e - k e η η ζ e i c h η e t ι that one as organic nitrogen base an aromatic, primary »secondary or tertiary amine used« 009834/1984 Jt 5. The method according to claim 1 and 2, a therefore ge, - indicates that the organic nitrogen base is an alicyclic primary, secondary or tertiary amine used. 6. The method according to claim 1 and 2, characterized in that one al-s organic nitrogen base uses a heterocyclic compound. 7. The method according to claim 1 and 2, characterized in that as organic A quaternary ammonium hydroxide or nitrogen base a quaternar ammonium halide is used. BATH ORIGINAL 009834/1984