DE2261081A1 - AMIDOMETHANE PHOSPHONIC ACID DERIVATIVES - Google Patents

Description

Bayer Aktiengesellschaft

Central area of patents, trademarks and licenses

509 Leverkusen. Bayerwerk B / He

Il 3rd Dec. 1972

Amidome thanphoaphonic acid derivatives

The invention relates to new amidomethanephosphonic acid derivatives the general. formula

h 9-

K Il .OR ₁

in the

R ₁ and R ₂ independently of one another represent hydrogen, an alkali metal, alkaline earth metal or ammonium ion, or preferably represent a C -, - C, alkylate optionally substituted by halogen atoms, in particular chlorine or bromine atoms, or together with the oxygen atoms and the phosphorus atom form a five- to seven-membered heterocycle,

R _{5 stands} for hydrogen, a Cj-Cg-alkyl or C ₅ -C ₆ -alkenyl radical, or for the radical

/ ₁

o-E. · Stands', and

POR ₂

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R is an acyl radical of the formula RO-CO- or Rc-SO ₂ - means in which

B .. for an optionally substituted Cj-C ^ -alkyl-C ₂ -C ₂₀ -alkenyl, cycloalkyl, aralkyl or aryl, preferably a Cj-Cg-alkyl or C ₂ -C / - which is optionally substituted by halogen atoms -Alkenyl radical, or a radical of the formula Rg- (CH ₂ -CH-O) _n -CH ₂ -CH-βtent, in which IU R-,

Rg a C ₁ -C ₂₀ alkoxy, Cj-CgQ

Cycloalkoxy or an optionally substituted aryloxy, a C ^ -C ₂ Q-alkylthio or Cj-CgQ-acylaminoreet,

R "hydrogen, or a lower alkyl radical, preferably a methyl group, and

η is a number from 1 to 40; and

Rc represents an optionally substituted C.-C _{? O} -alkyl, C, -C ₂₀ -alkenyl radical or aryl radical;

and a process for the preparation of the compounds of Formula (I).

For R, for example:

as C ^ Cgg-Alkylreete: the methyl, ethyl, n-propyl, sec.Butyl-r, i-hexyl-, n-decyl-, n-hexadecyl-, n-octadecyl- and n-eicosyl residue.

possible substituents for these radicals are:

the hydroxyl group, alkoxy groups, such as the methoxy, xthoxy and butoxy group; Acyloxy groups, such as the formyloxy, acetoxy

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and benzoyloxy group; Aminocarbonyloxy groups such as the aminocarbonyloxy, N-methylaminocarbonyloxy and N, N-diethylaminocarbonyloxy groups; Alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and n-hexoxycarbonyl groups; Carbonamido groups such as the carbonamide, N-methyl carbonamide, Ν, Ν-diethylcarbonamide and N-hexylcarbonamide group; Alkylsulfinyl groups such as methylsulfinyl and ethylsulfinyl; Alkanesulfonyl groups such as methanesulfonyl and ethanesulfonyl groups; Acyl groups, such as the alkanecarbonyl and benzene carbonyl groups, eg acetyl, propionyl, hexanecarbonyl, benzoyl and toluyl groups; also carboxyl and nitrate groups; but in particular halogen atoms, such as chlorine or bromine atoms, as C ₂ -C ₂ Q-alkenyl radicals: the vinyl, allyl, decenyl and octadecenyl radical; suitable substituents in the above as substituents for the CJC ₂ 2 ~ ^A l ^lc y ^{lres' te} listed groups, preferably halogen atoms such as chlorine or bromine atoms, into consideration;

as cycloalkyl radicals: the cyclopentyl and cyclohexyl radical and as substituents for these radicals, lower alkyl groups, e.g. methyl and tert. Butyl groups, also halogen atoms such as the chlorine atom;

as aralkyl radicals: the benzyl and ß-phenylethyl radical and as Substituents of lower alkyl groups such as the ethyl group, and also halogen atoms such as the chlorine atom; as aryl radicals: the phenyl radical and phenyl radicals substituted by lower alkyl groups and / or halogen atoms such as the Tolyl and xylyl radicals and the chlorophenyl and dichlorophenyl radicals.

For example, the following are mentioned for Rg:

as σ ₁ -σ ₂₀ · " ^{Α1ΙεοχνΓββ} * ^{β: the} methoxy, ethoxy, hexoxy, dodecyloxy and octadecyloxy radical;

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as C ₁ -C 2 Q alkenyloxy radicals, in particular the allyloxy radical; as cycloalkoxy radicals: the cyclohexyloxy, methylcyclohexyloxy and dimethylcyclohexyloxy radical;

as aryloxy radicals: the phenoxy radical and the _{phenoxy radicals substituted by C 1} -C ₂₂ -alkyl groups and / or halogen atoms, such as the cresoxy, xylenoxy, nonylphenoxy, dodecyclphenoxy, chlorophenoxy and dichlorophanoxy radical; as C ₁ -C ₂ Q-alkylthio radicals: the methyl mercapto, ethyl mercapto, n-hexyl mercapto and dodecya mercapto radical; as C ^ CgQ acylamino radicals: the acetylamino, propionylamino, butyrylamino, dodecanecarbonylamino and heptadecanecarbonylamino.

For example, the following can be mentioned for Rc:

as Cj-CgQ-alkyl radicals: the methyl, ethyl, butyl, octyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl and octadecyl radical and their mono-, di- or trinalogen substitution products, such as the Chloromethyl, 2,3-dibromopropyl _T> monochloropentadecyl, dichlorohexadecyl and trichlorohydoxadecyl radical.

as C ₁ -C 2 Q-alkenyl radicals: the allyl, hexenyl, decenyl and octadecenyl radical and their halogen substitution products; as aryl radicals: the phenyl and naphthyl radical and the phenyl radicals substituted by Cj-C ^ -alkyl groups, halogen atoms, nitro groups or carboxyl groups, such as the tolyl, xyIyI, t-butylphenyl, nonylphenyl, dodecylphenyl and chlorophenyl radical.

The compounds of the formula (I) are prepared by that one N-acylamlnomethyl derivatives of the general Formula (II)

R ₈
RH-CH ₂ X II,

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in the

R has the meaning given above,

X for an acetoxy or propionyloxy radical, for a Halogen atom, especially a chlorine atom, or a hydroxyl group, and

Rg represents hydrogen, a Cj-Cg-alkyl or C, -Cg-alkenyl radical or the radical -CH ₉ -X,

with phosphorous acid trialkyl esters of the formula

₁₀ III

■ ^0R 11

in the

Rq, R ₁₀ and R ₁₁ independently of one another represent a Cj-C-alkyl radical optionally substituted by halogen atoms, or Rq and R ₁₀ together with the oxygen atoms and the phosphorus atom form a five- to seven-membered heterocycle,

optionally in an inert diluent under the reaction conditions at temperatures of 40-160 ⁰ C, preferably 60-130 ⁰ C, is reacted.

The compounds of the formula I in which R ₁ and / _{or R 2 are} hydrogen or an alkali metal, alkaline earth metal or ammonium ion are obtained in a known manner by dealkylation or by hydrolysis of the phosphoric acid esters; see for example Houben-Weyl "Methods of Organic Chemistry" 4th edition 1963, Vol. 12/1, pp. 410-412.

Examples of representatives of the phosphorous acid trialkyl esters of the formula III include:

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Trimethyl phosphite, triethyl phosphite, dimethyl ethyl phosphite, Tri-ieopropylphoephit, tri-n-prophylphospht, dimethyl-n-propylphoephit, trl-n-butylphoephit, tri-ieo-butylphoephit, Tri- (chloroethyl) phosphite, tris (bromoethyl) phoephite, 2-methoxy-1,3-dioxa-phospholane, 2-ethoxy-4-methyl-1,3-dioxaphoepholane.

As a representative of the N-acylaminomethyl compounds of the formula II selenium named for example:

N-hydroxymethyl-ethyl urethane, H-hydroxymethyl-n-butyl urethane, N-hydroxymethyl-n-dodecyl urethane, R, N-Bie- (hydroxymethyl) ethyl urethane, N-acetoxyfliethyl methyl urethane, H-acetoxymethyl ethyl urethane, N-methyl-N- chloromethyl-methyl urethane, H-räthyl-N-chloromethyl-ethyl urethane, N-allyl-H-chloromethyl-ethyl urethane, N-methyl-H-chloromethyl-allyl urethane, N-methyl-H-chloromethyl-chloroethyl urethane, If-methyl-N- chloromethyl-n-butyl urethane, N-methyl-H-bromomethyl-n-decyl urethane, H-methyl-M-chloromethyl-n-dodecyl urethane, I-methyl-N-chloromethyl-2,3-dil> romopropyl urethane, H-methyl-N- chloromethyl-bensylurethan, N-methyl-N-chloromethyl-phenyl-urethane, N _f H-PIP (chloromethyl) -methylurethan _t N, N-bending (chloromethyl) -äthy urethane!, H, H-bending (chloromethyl ) -nbutyl urethane, N, H-Bia- (chloromethyl) -n-octyl urethane, N, H-Biβ- (chloromethyl) -n-dodecyl urethane, N _T N-bis (chloromethyl) -neicoayl urethane, N _t N-Bi8- (Chloromethyl) allyl urethane, N, H-BIs- (chloromethyl) -2,3-dlbromopropyl urethane, H, H-Bie- (chloromethyl) beneyl urethane, H-methyl-H-chlorine methyl-n-lauroxy-tetraethoxy urethane, N-methyl-H-chloromethyl-nonylphenoxyhexaethoxy urethane, H, H-B1b- (chloromethyl) -octadecyloxydecaethoxy urethane, H-hydroxymethyl-methanesulphonamide, N-hydroxymethyl-butane sulphonamide, H-octane sulphonamide, N-octane sulphonamide Hydroxymethyl-pentadecanesulfonamide, H-Hydroxy-methyl-beniolaulfonamide, H-hydroxymethyl-

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toluenesulphonamide, N-methyl-N-chloromethyl-methaneulphonamide, N-methyl-N-chloromethyl-ethanesulphonamide, N-methyl-N-chloromethyl-butanesulphonamide, U-methyl-Jf-chloroethyl-pentadecanesulphonamide, N-ethyl-N-chloromethyl- pentadecanaulphonamide, If-methyl ~ N-chlomethyl-chloromethanesulphonamide, tf-methyl-N-chloromethyl-mono-chloropentadecanesulphonamide, IT _t ir-bis- (chloromethyl-methanesulphonamide, H, N-bis- (chloromethyl) -ethaneilfonamide, N, N-Bi- (chloromethyl) -butanesulfonamide, N, H-bis- (chloromethyl) -octanesulfonamide, N, N-bis- (chloromethyl) -pentadecanesulfonamide, N, N-bis- (chloromethyl) -chloromethanesulfonamide.

As examples of the compounds according to the invention bsw. The compounds of the formula I which can be prepared by the process according to the invention are listed in those R, R ..., Rp and R, those given in the table below Have meaning.

R fi-j R2 R3

CH ₃ O-CO C ₀ H ₁ -OCO-

C ₂ H ₅ O-CO-

C _o H _c 0C0-2 5

C ₂ H ₅ O-CO CH ₅ O-CO-

C_H _C O-CO-2 5

CH ₅ OE, - H H H H CH ₃ - CH ₃ - H C ₂ H ₅ - C ₂ H ₅ - H ClCH ₂ CH ₂ - ClCH ₂ CH ₂ - H OE, CH ₃ CH ₃ O ₂ H C ₂ H CH ₅

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C ₀ H ₅ O-CO

CH OCO-CH OCO-

C ₀ H.0CO-2 5

C H OCO-

C HqO-CO

5 ClCH, "2 2261081 CH, CH, ₂ CH ₂ - CH ₂ -CH-CH ₂ - CH, -CH ₂ P (OCH)
O "1 CH, -CH ₀ P (OCH)
0 ClCH ₂ CH ₂ - C ₂ H ₅ -CH ₂ P (O-C ₂ H ₅ ) ₂
0 CH, O CH, 1/2 CH, -CH ₂ P (OCH ₃ ) ₂ CH, C ₂ H ₅ CE, ° ^ ONa
-CHpP
^V OCH C ₂ H C ₂ H ₅ CH, CH ₃ K CH, CH ₃ CH, OH, OH, 2 ^ 0Ca 1/2
CH ₂ -P
^N OCH ₃ N / A CH, CH, C ₂ H ₅ 0
-CH ₂ P (OC ₂ H ₅ J ₂ N / A C ₂ H ₅ OH, Approx CH, CH CH,

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R, R,

NH ₂ C (O) OCH ₂ CH ₂ OCO-

) ₅ -0C0- CH ₃

^CH 3

CH. CH,

CH,

CH,

CH,

It

-CH ₀ P (OCH,), CH ₅

CH ₂ = CH-CH ₂ OCO-

CH, CH,

CH ₂ = CH-CH ₂ OCO-CH ₂ = CH-CH ₂ OCO-

CH ₂ = CH-CH ₂ OCO-

C ₁₈ H ₅₅ OCO-

BrCH ₂ -CH ₂ CH ₂ OCO-Br

OH, 0 OH, OH, -CH ₂ P (OCH ₅ ) 2 OH, C ₂ H ₅ CH ₂ = CH-CH ₂ - O ₂ H ₅ OH, OH, OH, -OH ₂ P (O) (OCHj) ₂

CH, CH,

BrCH ₀ CH-CH ₀ OCO-

² I ²

Br

CH, CH,

CH,

BrCH ₂ CH-CH ₂ QCO-Br

C ₂ H ₅

BrCH ₂ CH-CH ₂ OCO-Br

CH. CH

-CH ₂ P (OCH ₅ ),

BrCH ₀ CH-CH ₀ OGO-Br

C ₂ H

-CH ₂ P (0C

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R,

R,

BrCH CH-CH -OCO-

Br

ClCHgCH ₂ -

ClCHgCHg CH ₅

ClCHgCHgOCO- CH, CH-

CH,

CH,

CH,

Cl ₅ CCH ₂ OCO

CB, CH, 0
-CHgP (OCH > 2 CHgCHgCl CHgCHgCl 0
-CHgP (OCHg CH ₂ Cl) ₂ CH CH 0
-CHgP (OCH ₅ H

CH-

CH,

CH,

CH,

CH,

O η

-CH ₂ P (OCH ₅ )

CHjOCHgCHgOCO- CH

CH,

CH,

CgH ₅

C ₂ H ₅

O η

-CH ₂ P (OC ₂ H ₅ )

OCO-

CH,

CH,

CH,

(/ VoCHgCHgOCO- C ₂ H ₅

CH ₁

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R. * 1 ^R 2 ^R 3

CH SOg-CH SOg-CH ₅ SO ₂ -CH ₅ SO ₂ -CH-SOg-

CH SOg-

CH SOg-

SO ₂ -

CH ₅

CH ₅ CH, CH ₃ 0 C ₂ H ₅ ° 2 ^E 5 H -CH ₂ P (OCH ₅ ) ₂ C ₂ H ₅ -C ₂ H ₅ CH, -CH ₃ C ₂ H ₅ -C ₂ H ₅ CH-CH-CH ₂ - CHg = CHCHg- ClCHgCHg- ClCH ₂ OH ₂ - 0
-CHgP (OC ₂ H ₅ ; N / A CH ₃ CHg = CH-CHg- -C ₃ H ₇ 0 OH, CH ₃ -CH ₂ P (OCH ₃ ) g O C ₂ H ₅ C ₂ H ₅ - -CHgP (OC ₂ H ₅ ) CH, CH ₅ H C ₂ H ₅ C ₂ H ₅ CH, OH, CH ₅ . CH, CH ₃ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ CH, N / A

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CH-CH, Na Approx

CH, CH. N / A

1/2

CH,

CH,

CH,

CH ₁

CH,

CH,

OH,

CH,

C ₂ H ₅

(I.

-CH ₂ -P (OCH ₃ ) ₂ H

CH,

N / A

CH,

CH,

CH,

CH

CH,

CH,

CH,

CH ₂ -P (OCH ₃ ) ₂

S / OCH,

-CH ^ -P

2 \

ONa

CH ₅ -CH ₂ -P (OCH) ₂

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^CH 3 \ - /

R ₂ ^R 1 C ₂ H ₅ C ₂ H ₅ C ₂ H ₅ C ₂ H

R,

O _n -

ClCHgSO ₂ -

ClCH ₂ SOg-

³ 2 ^H 5

C ₂ H ₅

CH,

CH,

CH,

C "H _C

CH,

It

-CH ₂ P (OCH ₃ )

CH,

CH

-CH ₂ P (OCgH ₅ )

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CHgCH ₂ Cl

409826/1128

In the inventive implementation of the compounds of
Formula II with the phosphorous acid trialkyleetem of the formula III, it is expedient to _{continuously remove the compounds R 11} -X formed in the reaction, for example methyl chloride, ethyl bromide or methyl acetate, from the reaction mixture, for example by distillation or by a stream of inert gas. In general, the compounds of the formulas II and III are used in equivalent amounts, based on the -CHpX groups contained in the molecule of the N-acylaminomethyl compound (II), but the trialkyl phosphates III can also be used in slight excess.

Examples of diluents which are inert under the reaction conditions are toluene, xylene, n-nonane or dimethylformamide called.

The compounds of the formula I are capable of many uses. They can be used e.g. as flame retardants for organic Materials such as textiles, wood, plastics, paper, as dyeing and printing auxiliaries, as textile auxiliaries, as surface-active substances, lubricating oil additives and as Pesticides, or used as intermediates for such agents.

For the parts given in the following examples
it is parts by weight, unless otherwise
is specified.

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example 1

577 parts of triethyl phosphite are at 100-110 ⁰ G slowly added 285 parts !!, If-Bie-ichlormethylJ-earbaminsäuremethylester. The resulting ethyl chloride is collected in a cold trap. After completion of the addition for 1 hour at 120 130 ⁰ C is reheated. The volatile constituents are then distilled off first at 10-20 torr, then at 1 torr. Distillation over a thin film evaporator at 0.4-0.5 Torr (bath temperature 180 ° C) gives 532 parts (92 # of theory) of the compound of the formula

0 p

CH ₂ P- (OC ₂ H ₅ ) ₂ O

obtained as a colorless liquid. £ ° 1.4492

P ₂ (MC 375)

Calc .: C 38.4 t H 7.2 # N 3.74 * P 16.5 Found: C 38.4 $ H 7.5 1> N 3.70 56 ρ 16.9

Example 2

161 parts of trimethylphosphite are added dropwise at _{80-90 ° C. with 107 parts of IT for} bis (chloromethyl) allyl urethane.

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The resulting methyl chloride is passed through a cooler into a cold trap. Fold end of the addition is 1 hour at 80 - 9O ⁰ C stirred. The volatile constituents are then distilled off ^{at 100 ° C. in a water jet vacuum.} The residue is then on a thin film evaporator at 190 bond of the formula

damper at 190 - 200 ⁰ C and 0.8 Torr. The Ver-

CH ₅ = CH-CH ₅ -O-CO-X

^{ά ά}

0 CH ₂ -P (OCH,)

CH ₅ -P (OCH,) ₅ 0

is obtained as a colorless liquid.

1.4490

.HOoP ₉ (MG 345)

Calc .: C 34.7 H 6.1 P 18.0 Found: C 34.0 H 6.3 P 19.1

Example 3

146 parts of triethyl phosphite are at 80 - 90 ⁰ C slowly versetet with 74.3 parts of N, N-bis (chloromethyl) -äthylurethan. The resulting ethyl chloride is collected in a cold trap. After the addition is complete a further 1.5 hours at 110 - 115 ⁰ C stirred. The phosphite excess is at 110 - 120 ⁰ C distilled off and 12 Torr. The phosphonate of the formula is obtained by distillation over a thin film evaporator

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• ο

/ CH ₂ P (OC ₂ H ₅ ) ₂

²⁵ '° "^ CH ₂ P (OC ₂ H ₅ ) ₂
0

obtained in 90 # yield as a colorless liquid. n £ °: 1.4490
C ₁₃ H ₂₉ NO ₈ P ₂ (MG 389)

Calc .: C 40.2 H 7.46 N 3.6 P 15.9 Found: C 40.6 H 8.10 N 3.6 P 16.1

Example 4

In a veraehenen with a beheinten at 60 ⁰ C column, dropping funnel, stirrer, thermometer and gas inlet tube piston 285 parts of trimethyl phosphite at 100 to - 120 ⁰ C presented. At this temperature, parts of N-acetoxymethyl-carbamic acid ätliylaster are allowed to drip down within 2-3 hours. The methyl acetate formed was distilled off over the column with the aid of a gentle stream of nitrogen. When the addition is complete, the temperature of the reaction mixture is increased to 130 - HO ⁰ C and held until no more ethyl acetate distills off. Excess trimethyl phosphite is distilled off in vacuo. The flask residue is distilled over a short column. There will be 253 parts ( $ 62.5> of theory) of the compound of the formula

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G ₂ H ₅ O-CO-IIH-CH ₂ P- (OGH ₃ ) ₂

obtained as a colorless liquid. Bp: 148-150 ° / 0.5 Torr

: 1.4506
C ₆ H ₁₄ NO ₅ P (MG 211)

Calc .: C 34.2 H 6.63 N 6.63 P 14.65 Found: C 34.8 H 6.80 N 6.60 P 14.60

Example 5

410 parts of methyl N, N-bis (chloromethyl) carbamine acid are slowly added to 1285 parts of tris (chloroethyl) phosphite at 100-115 ° C. under a vacuum of 20-30 torr. The resulting Äthylenckilorid is collected in a cold trap. After the addition is complete ^{, the mixture is heated to 130 - HO 0} C at 10-20 torr until no more ethylene chloride condenses. To remove volatile by-products, the mixture is heated to 120 ° C. at 0.1 torr for a further 2 hours. Eb will be 1260 parts ( $ 80> of theory) of the phoaphonate of the formula

(I.

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as a colorless liquid which is replaced by distillation.

n £ °: 1.4932

(MG 513)

Calc .: C 28.0 H 4.47 Cl 27.7 P 12.05 Found: C 27.9 H 4.60 Cl 28.1 P 12.10

Example 6

360 parts of N, N-bis (chloromethyl) -butylurethan be at 100-120 ⁰ C was added dropwise to 450 parts of trimethyl phosphite added. Here, 150 parts of methyl chloride are evolved within 5 hours, which are collected in a cold trap. Excess phosphite is distilled off at 12 Torr and 110 120 ^{° C.} The residue is purified by heating for two hours at 110 - free 120 ⁰ C at 0.1 torr of volatile by-products. There are 95 96 d. Th. Obtain a colorless oil which, according to the gas chromatogram, is 97 # from the phosphonate of the formula

C, H _Q O-CO-N.
^{4 y}

consists.

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n £ °: 1.4585
C ₁₂ H ₂₅ NO ₈ P ₂ (MG 361)

Calc .: C 36.6 H 6.9 P 17.1 Found: C 36.1 H 6.8 P 16.6

BelBplel 7

Into a flask equipped with stirrer, thermometer and reflux condenser is allowed at 90-100 ⁰ C ewei from separate dropping funnels 127 parts of NN-bis-CchlormethylJ-carbaminefture-2,3-dibrompropylester butropfen and 89 parts of trimethyl phosphite. The methyl chloride formed is caught in a cold trap. After completion of the addition for 1/2 hour at 110 ⁰ C and then at 10-12 Torr eunächst erhitet 1 hour at 100 ⁰ C. There are 188 parts of the compound of formula

,, CH ₂ P (OClOp BrCH ₉ -CH-CHp-OCN ^{ά 5 ά}

Br 0

in the form of a non-distillable, yellow, viscous Get liquid.

n £ °: 1.4962
C ₁₀ H ₂₁ Br ₂ NO ₈ P ₂ (MW 505)

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Calc .: G 23.8 H 4, Ί Ρ 12.3
Found: C 24.5 H 4.3 P 12.3

Example 8

The solution of 146 parts of N-hydroxymethyl-methanesulfonamide in 40 parts of ethanol is the same with 193 parts of triethyl phosphite in a 120 - 130 ⁰ C dropwise geheifcten flask. The ethanol is distilled off through a column. The reaction temperature is increased up to 180 ⁰ O; a total of 82 parts of ethanol distilled off. The volatile compounds are then removed from the reaction product by heating to 150 ^{° C. in vacuo.} There are 261 parts of the phosphonate of the formula

obtained as a residue in the form of a dark brown viscous liquid.

C ₆ H ₁₆ NO ₅ PS (MG 245)

Calc .: N 5.71 # P 12.67 $ S 13.08 £ Found: N 5.56 # P 12.75 # S 12.70 $

Example 9

100 parts of triethyl phosphite are at 70-80 ⁰ C in portions with 58 parts of N, N-bending (chloromethyl) -3aethansulfonamid veraetet. The reaction mixture is erhitet to 120 ⁰ C, until the development of ethyl chloride terminated. "Overall,

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55 parts of ethyl chloride are caught in an oil trap. The reaction odor is freed from the volatile constituents by heating in vacuo to 10O ^{0 C.} Eb 101 parts of a yellowish, viscous, non-distillable liquid of the formula remain as residue

cn, -so.-r

: 1.4602
C ₁₁ H ₂₇ NO ₈ P ₂ S (MG 397)

Calc .: N 3.53 l · P 15.62 # S 8.07 1> Found: N 3.74 + P 15.60 # S 8.10 £

Example 10

Following the procedure described in Example 9 operation is obtained from N, N-bis (chloromethyl) -methanesulfonamide and trimethyl phosphite, the compound of formula

CH, -SO ₉ -IL ^{fc J 0 c} CH ₉ -P (OCH,),

0 received.

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C ₇ H ₁₉ NO ₈ P ₂ S (MW 339.3)

At · .: N 4.13 0? 18.27 # S 9.46 #
Found: N, 4.10 <j> P $ 18.25 S $ 9.38

Example 11

The solution of 72 parts of N, N-bis (chlomethyl) -ehlorifiethansulfonamid in 170 parts of xylene is carried out at 90-90 ⁰ C langeam mixed with 86 parts Trimethylphosph.it. Subsequently, the temperature is 110 - 120 ⁰ C increased until the development of methyl chloride ends. A total of 32 parts of methyl chloride are collected. The volatile compounds are distilled off in vacuo from the reaction mixture. 112 parts of a viscous residue remain, which crystallizes after trituration with water.
SchmelBpunkt: 77 - 79 ⁰ C

Cl-CH ₉ -SO ₉ -N.

0
/ JH ₂ -P (OCH,)

CH ₂ -P (OCH ₃ )
0

C ₇ H ₁₈ ClNO ₈ P ₂ S (MG 374)

Calc .: Cl 9.49 # N 3.74 96 P 16.59 $> S 8.56 Found: Cl 9.35 $ N 3.65 $ P 16.72 # S 8.10

Example 12

628 parts of N-hydroxymethyl-p-chlorophenylsulfonamide are with

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44-0 parts of triethyl phosphite slowly heated to 110-120 ° C. The resulting ethanol is distilled off through a column. The temperature of the reaction mixture is gradually increased to 150 - 160 ⁰ C increased. After the evolution of ethanol has ended, the reaction mixture is freed from the volatile compounds in vacuo. 915 parts of the phosphonate of the formula remain as residue

0 C VSO ₂ NH-CH ₂ -P (OC ₂ H ₅ ) ₂

in the form of a brownish viscous liquid. C ₁₁ H ₁₇ ClNO ₅ PS (MG 342)

Calc .: N 4.09 # P 9, Θ6 # Found: N 4.08 # P 8.45 1 »

Example 13

80 ⁰ C, 130 parts of N, N-bis (chloromethyl) -sulfonamide dropwise hineugefügt which has been from the technical Sulfochlorierungsprodukt a Alkangemi s see with an average of 15 carbon atoms made - to 91 parts of trimethyl phosphite are at 70. The resulting methyl chloride is collected in a cold trap. After complete addition, the reaction mixture is continued for 1 hour at 90 - 100 ⁰ C and then stirred in vacuo at 100 - 11O erhitet ⁰ O to remove volatile compounds bu. 160 parts of a phosphonate of the formula remain

Le A 14 749 - 24 -

BATH ORIGINAL

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_^10-15

in the form of a reddish-brown liquid that gives clear, foaming solutions in water.

n £ °: 1.4641

P ₀ S (MG 535).

Calc .: N 2.62 0 S 5.98 £ P 11.58
Found: N 2.30 0 S 5.90 56 P 10.50

Example 14

87 parts of trimethyl phosphite are at 70-80 ⁰ C is added dropwise a solution of 164 parts of N-methyl-N-chloromethyl-octansulfonamid in 170 parts of xylene. The methyl chloride formed is caught in a cold trap. After complete addition, the reaction mixture is stirred first for 1 hour at 90 100 ⁰ C and then by heating at 100 - 110 ⁰ C freed from solvent in vacuo and volatile compounds. 193 parts of the phosphonate of the formula remain as residue

I! Y — SOp-N-CHp ""

CH ₃

Le A 14 749 - 25 -

0-9 8 2.6 / 1 128

in the form of a reddish liquid.

: 1.4705
C ₁₂ H ₂₈ NO ₅ PS (MG 329)

Ber .: N 4.26 <j> P 9.42 £ S 9.72 £ Found: N 4.33 # P 9.10 <f> S 9.40 #

Example 15

80 ⁰ C, 115 parts of N-allyl-N-chloromethyl-carbamideäuremethyleeter dropped - To 100 parts Trimethylphosph.it and 0.5 part of hydroquinone are at 70th The resulting methyl chloride is collected in a cold trap. After complete addition, the reaction mixture is sunächst one hour at 80 - 9O ⁰ C gerührt.und then distilled in vacuo. There are 151 parts of the phosphonate of the formula

CH ₂ -CH = CH ₂ O CH ₃ OOC-N CH ₂ P (OCH ₃ ) ₂

obtained as a colorless liquid. Ip: 99-101 ⁰ C / 0.1 Torr

: 1.4600
C ₈ H ₁₆ NO ₅ P (MG 237)

Calc .: C 40.55 t H 6.8 £ N 5.91 t P 13, o7 % Found: C 40.90 # H 7.0 t N 5.90 <fi P 12.90 Jt

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Example 16

80 ⁰ C, 276 parts of N-methyl-N-chloroethyl-earbamidsäure-methylester was dropped - to 248 parts at 70 Trimethylphoephit be. The methyl chloride formed is caught in a cold trap. After complete addition, the reaction mixture is first for 1 hour at 90 - stirred 100 ⁰ C and then distilled in vacuo. There are 309 parts of the phosphonate of the formula

CH ₃ OOC-N-CH ₂ -P (OCH ₃ ) ₂ CH ₃

obtained as a colorless liquid. Bp: 92 - 95 ° C / 0.07 Torr n £ °: 1.4510 C ₆ H ₁₄ NO ₅ P (MW 211)

Calc .: C 34.13 f> H 6.64 $ N 6.64 $> P 14.69 # Found: C 34.40 $> H 6.70 56 N 6.70 56 P 14.40 #

Example 17

90 ⁰ C, the solution of 230 parts ö- (carbonamido-oxy) ethyl-N-methyl-N-chlormethylurethan added dropwise in 200 parts of dimethylformamide - To 150 parts of trimethyl phosphite is at 80th The methyl chloride formed is caught in a cold trap. To

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completion of the addition the Reaktionemischung is heated for 1 hour at 10O ⁰ G and then freed in vacuo at 10O ⁰ C and 1 Torr of volatile Beetandteilen. Ee are 302 parts of the phosphonate of the formula

0 0 0

Ii Il Il

NHU-CO-CH ₀ CH ₀ -OCN-CH ₅ -P,

c Cc. \ C.

obtained as a colorless viscous liquid. C ₈ H ₁₇ N ₂ O ₇ P (MW 284)

Calc .: C 33.8 H 5.99 N 9.86 P 10.9 Found: C 34.3 H 6.40 N 9.60 P 10.3

Example 18

55 parts Tria'thylphosphat be at 120 - 13O ⁰ C was added 96 parts of N-Hydroxymethylamids, which in a conventional manner from the Sulfamic! of a technical sulfochlorination product of an alkane mixture with an average of 15 carbon atoms. The temperature of the reaction mixture is heated to 140 - 150 ⁰ C increases and ethanol formed is distilled off at the nitrogen atom. After the reaction has ended, the volatile constituents are distilled off under reduced pressure.
126 g of parts of a clear, reddish, vis-

pn

kosen liquid with a refractive index nT; I.46OI

C ₁ 5-H ₅₁ -SO ₂ -NH-CH ₂ -P- (OC ₂ H ₅ )

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(MG 440)

Ber .; P: 7.05 # N: 3.18 ^ S: 7.27 %

Found: Pi 6.8 % N: 3.0 £ S: 7.5 Ji

120 parts of the compound are diluted with 25 parts of ethanol, and a solution of 10.5 parts of sodium hydroxide in 15 parts of water is added. The mixture is 2 hours at 80 - 9O ⁰ C stirred. The clear solution is strongly acidified with hydrochloric acid; the organic phase is separated off and washed again with aalzsaurehal.tigem water and then evaporated in vacuo. 83 g of parts of the phosphonate of the formula remain

C ₁₅ H ₃₁ -SO ₂ NH-CH ₂ -P-OC ₂ H ₅

\)H

in the form of a viscous oil.
C ₁₈ H ₄₀ NO ₅ PS (MG 413)

Ber. · N: 3.39 <f> P: 7.5 # S: 7.74 Found: N: 3.1 $> P: 7.1 $> S: 7.9

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Claims (6)

Patent claims: in the R ₁ and Rp independently of one another represent hydrogen, an alkali metal, alkaline earth metal or ammonium ion, or a C 1 -C 4 -alkyl radical optionally substituted by calogen atoms, or E together with the oxygen atoms and the phosphorus atom form a five- to seven-membered heterocycle, R, for hydrogen, a Cj-Cg-alkyl or C, -C / - alkenyl radical, or for the radical ^ ₁ -PW - P ² ti ^x no, and 0 ^0R 2 R is an acyl radical of the formula RO-CO- or Rc-SO ₂ - in which R. for an optionally substituted Cj-Cp ₂ "alkyl, C ₂ -C ₂₀ -alkenyl, cycloalkyl, aralkyl or aryl radical or a radical of the formula R _c - (CH ₀ -CI-O) _1n - is in which ο c. \ η R ₇ R _{6 is} a C ₁ -C ₂₀ -AlkOXy-, C_-C ₂₀ -Alk6nyloxy-, Le A 14 749 - 30 - 409826/1128 Cycloalkoxy or an optionally substituted one Aryloxy, a Cj-CgQ-alkylthio- or Cj-Cp ^ -acylamino radical, R _{7 is} hydrogen, or a lower alkyl radical and η is a number from 1 to 40; and represents an optionally substituted GJC ₂ Q "alkyl, C, -G ₂₀ -alkenyl radical or aryl radical, 2. Amidomethanphoephonsäure derivatives according to claim 1, characterized in that R, and R _{5 have} the meaning given in claim 1 and
R ₁ and Rp independently of one another represent a C ₁ -C alkyl radical optionally substituted by chlorine or bromine atoms and Rj is an optionally substituted by halogen atoms - or C ₂ -Cg -alkenyl radical. 3. Process for the preparation of amidomethanephosphonic acid derivatives the formula ι 3 κ
RN-CH ₉ -Pv ^ά OR ₂ in the R ₁ and R ₂ independently of one another represent hydrogen, an alkali metal, alkaline earth metal or ammonium ion, or a C ₁ -C alkyl radical which is optionally substituted by halogen atoms Le A 14 749 - 31 - 4098 26/1128 stand, or together with the oxygen atoms and the Phosphorus atom is a five- to seven-membered heterocycle form, R, for hydrogen, a C ₁ -C ₆ -AlCyI- or C ^ -Cgrest, or for the remainder / ₁
-CH, ~ .Έ. stands, and Ό ^0R 2 R is an acyl radical of the formula R-O-CO- or Rc means in which R- for an optionally substituted O ₁ -C ₂₂ -alkyl, C ₂ ~ C ₂ Q-alkenyl, cycloalkyl, aralkyl or aryl radical or a radical of the formula R ₆ - (CH ₂ -CH-O) _n - stands in the k ₇ R _{6 is} a C ₁ -C ₂₀ -AlkOXy-, C ^ -CgQ-alkenyloxy-, Cycloalkoxy or an optionally substituted aryloxy, a C ^ CgQ-alkylthio or C ₁ -C ₂ Q-acylaminoreet, R _{7 is} hydrogen, or is a lower alkyl radical and η is a number from 1 to 4-0; and Rc for an optionally substituted C-j-C _- Alkyl, C ^ -CjjQ-Alkenylreet or Arylcest, characterized in that one acylaminomethyl derivatives of formula Le A H 749 - 32 - 409826/1128 I ⁸ RN-CH ₂ -X in the R has the meaning given above, X is an acetoxy or propionyloxy radical, for a Halogen atom or a hydroxyl group, and Rg represents hydrogen, a Cj-Cg-alkyl or C ~ -Cg-alkenyl radical or the radical -CH ₂ -X, with phosphorous acid trialkyl esters of the formula / ^0R 9 : io ^0R 11 in the Rq, R ₁₀ and R ^ ₁ independently of one another represent a C 1-6 alkyl radical optionally substituted by halogen atoms, or R _q and R ₁₀ together with the oxygen atoms and the phosphorus atom form a five- to seven-membered heterocycle. form, optionally in an inert diluent under the reaction conditions at temperatures of 40 - 160 ⁰ C and umsetet BAW dealkylated in a known manner, if appropriate, the thus obtained Phoephonsäureester. saponified. 4. The method according to claim 3, characterized in that N-acylaminomethyl derivatives in which R is a 4- OC-alkyl or Cg-Cg-alkenyl radical, Le A 14 749 - 33 - 40 98.26 / 1-128 with phosphorous acid trialkyl esters in which Rq, Rq and R ₁₁ independently of one another represent a C. ₁ -C - alkyl radical which is optionally substituted by chlorine or bromine atoms. 5. The method according to Anepruch 3 and 4, characterized in + that one uses K-acylaminomethyl derivatives in which X is a chlorine atom. 6. The method according to claim 3 to 5, characterized in that that may takes· that the Umsetrung at temperatures of 60 - 130 C pre- Le A 14 749 - 34 - 409826/1 128