Use of N,N-disubstituted phosphoryl carbamates and methods for their preparation

Abstract

The invention relates to the use of a compound of general formula I as a flame retardant.

Description

[0001] The invention relates to the use of N,N-disubstituted phosphoryl carbamates and a process for the preparation of N,N-disubstituted phosphoryl carbamates. It further relates to N,N-disubstituted phosphoryl carbamates.

[0002] Due to their high flammability, almost all polymer materials must be treated with flame retardants to prevent fires and minimize damage to people and property. In some cases, relatively large quantities of flame retardant, ranging from 10 to 25% by weight, must be added to the polymer materials to achieve sufficient effectiveness. Particularly effective flame retardants generate stable radicals in the gas phase, which terminate radical chain reactions in the flame. Halogenated flame retardants, i.e., compounds containing chlorine and bromine, exhibit this effect in particular. However, these halogenated flame retardants are often toxic, poorly biodegradable, and some are already banned by the European Union. Therefore, the general aim is to use halogen-free flame retardants.

[0003] Phosphorus-based flame retardants offer a significant alternative to halogenated flame retardants. Certain phosphorus compounds can generate phosphorus radicals that behave similarly to the aforementioned halogen radicals. Well-known examples include phosphoric acid derivatives and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives. Furthermore, phosphorus-based flame retardants can also suppress fire within the polymer matrix and / or on the polymer surface by forming low-volatility polyphosphates and phosphoric acids, as well as intumescent layers.

[0004] N-monosubstituted phosphorylcarbamate is known from CN 117736539 A and is said to be suitable as a flame retardant [1]. However, N-monosubstituted and unsubstituted phosphorylcarbamates exhibit properties that are disadvantageous for flame retardants. Flame retardants should have a long shelf life, be as unreactive as possible, be readily soluble in organic solvents, and not release toxic isocyanate upon heating. The synthesis of N-monosubstituted and unsubstituted phosphorylcarbamates is described in [2] to [8].

[0005] Furthermore, cost reduction is a key objective in the production of flame retardants. Environmentally friendly flame retardants are particularly desirable today. Such flame retardants are also referred to as "green" flame retardants.

[0006] The synthesis of carbamoyloxyphosphanes, i.e., trivalent phosphorus carbamates, from aminophosphanes and CO2 is known [5]. GB 991 979 A, ​​CH 422 777A and DE 11 72 260 B disclose the use of such compounds as insecticides and in synthesis [9-11]. These compounds have been oxidized with sulfur to N,N-disubstituted thiophosphoryl carbamates in the literature and patent literature.

[0007] Munoz et al. investigated the reaction of phosphoric acid (pseudo)halides, CO2, amines, and nucleophiles (alcohols, amines, thiols, azides, and cyanides) to form corresponding carbamoyl compounds, for example, cyclic carbamates, cyclic ureas, cyclic thiocarbamates, (di)carbamoyl azides, and cyanides [12-15]. They were able to identify phosphoryl carbamates as reactive intermediates. From

[12] and

[15] , procedures for the synthesis of isolated N,N-disubstituted phosphoryl carbamates are known, using ammonium carbamates prepared from CO2 as starting materials. However, the reaction conditions and work-up procedures used are not suitable for the synthesis of N,N-disubstituted phosphoryl carbamates with low oxidation states on the phosphorus, sterically unpredictable amines, or hydrolysis-prone phosphoryl carbamates. These compounds would not be possible in the reactions described by Munoz et al.The temperatures used may instead form aminophosphine oxide, or, if the product does partially form, it cannot be worked up in aqueous solution without decomposition. Additionally, the syntheses by Munoz et al. were only carried out on a milligram scale and are likely difficult to scale up. Finally, it should be noted that the compounds isolated by Munoz et al. were prepared from diphenylphosphoryl azide, which is explosive and releases toxic and explosive azides during reaction and workup.

[0008] The object of the invention is to eliminate the disadvantages of the prior art. In particular, compounds are to be identified that can be used as environmentally friendly flame retardants and are also long-lasting, as unreactive as possible, readily soluble in organic solvents, and do not release toxic isocyanate upon heating. Furthermore, processes for the production of these compounds are to be identified. Finally, a product comprising these compounds is to be identified.

[0009] This problem is solved by the features of claims 1, 10, 11 and 15. Advantageous embodiments of the inventions result from the features of the dependent claims.

[0010] According to the invention, the use of a compound of general formula I as a flame retardant is provided for, wherein R 1 and R 2are independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 18 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -O - and -N(R 5 )2 consists of, in which each R 5 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group or a substituted or unsubstituted aryl group, or R 1 and R 2together with the phosphorus atom, form a ring or ring system; and R 3 and R 4 are selected independently from the group consisting of a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group and a substituted or unsubstituted arylalkyl group, or R 3 and R 4 together with the nitrogen atom, they form a ring or a ring system.

[0011] The compound of general formula I is a pentavalent N,N-disubstituted phosphorylcarbamate. Phosphorylcarbamates are also known as phosphorus carbamates, carbamoyl phosphates, carbamoyloxyphosphine oxides, carbamoyloxyphosphates, carbamoyloxyphosphonates, or carbamoyloxyphosphinates.

[0012] The class of N,N-disubstituted phosphoryl carbamates has previously had no industrial relevance. In contrast to the better-known N-monosubstituted and N-unsubstituted phosphoryl carbamates, the compounds of general formula I can be obtained without the use of isocyanates, which are toxic and are produced from highly toxic phosgene. This will be described below, particularly in connection with the process according to the invention. The processes according to the invention enable the production of N,N-disubstituted phosphoryl carbamates from CO2 or compounds produced from CO2.

[0013] It has been found that the compounds of general formula I exhibit flame-retardant properties. Compared to N-monosubstituted and unsubstituted phosphorylcarbamates, they have a long shelf life at room temperature, are unreactive, particularly towards water, and are readily soluble in organic solvents. The inventors have conducted investigations and determined that the compounds tested do not release any toxic isocyanate upon heating. The compounds of general formula I are environmentally friendly flame retardants. In particular, they are halogen-free.

[0014] In the combination of the general formula I, R 1 and R 2Together with the phosphorus atom to which they are bonded, they form a ring or ring system. The ring or ring system can, in addition to the phosphorus atom, include at least one further heteroatom, wherein the further heteroatom is selected from the group consisting of oxygen, nitrogen, and sulfur. Preferably, the additional heteroatom is oxygen.

[0015] It may be provided that R 1 and R 2 Together with the phosphorus atom, they form a five- or six-membered ring to which no other ring, or one or more rings, are fused. R 1 and R 2Together with the phosphorus atom, a five- or six-membered ring to which one or more rings are fused is formed, resulting in a ring system. This ring system consists of two or more rings. Preferably, the ring system consists of two, three, four, or five rings, more preferably of two or three rings. Each of the rings can contain zero, one, or more heteroatoms, each independently selected from the group consisting of oxygen, nitrogen, and sulfur, with oxygen being preferred. Preferably, the fused ring(s) are five- or six-membered. Preferably, two fused rings are provided. The fused rings can be identical or different, preferably identical. The fused ring(s) can each be a benzene ring. In one embodiment, the compound of general formula I is a compound of general formula IA wherein R 3 and R 4which have meanings given in connection with the general formula I.

[0016] It may be provided that R 1 and R 2 are selected independently from the group consisting of a substituted or unsubstituted C1-C 12 -alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 12 -alkoxy group and a substituted or unsubstituted aryloxy group.

[0017] The ones related to R 1 , R 2 , R 3 and R 4 mentioned substituted or unsubstituted C1-C 18 The -alkyl group is preferably either a substituted or unsubstituted C1-C 12 -Alkyl group, more preferably a substituted or unsubstituted C1-C6 alkyl group and particularly preferably methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0018] The ones related to R 1 , R 2 , R 3 and R 4 mentioned substituted or unsubstituted C2-C 18 The -alkenyl group is preferably either a substituted or unsubstituted C2-C 12 -Alkenyl group, more preferably a substituted or unsubstituted C2-C6 alkenyl group and particularly preferably ethenyl, propenyl, butenyl, pentenyl or hexenyl.

[0019] The ones related to R 1 , R 2 , R 3 and R 4 mentioned substituted or unsubstituted C2-C 18 The -alkynyl group is preferably either a substituted or unsubstituted C2-C 12 -Alkynyl group, more preferably a substituted or unsubstituted C2-C6 alkynyl group and particularly preferably ethinyl, propynyl, butynyl, pentinyl or hexinyl.

[0020] In connection with R 1 and R 2 is a group -N(R 5 )2 provided, wherein each R5 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group or a substituted or unsubstituted aryl group. The two R groups 5 They can be the same or different. The rest R 5 is preferably a substituted or unsubstituted C1-C6 alkyl group. The R group is preferred. 5 selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl and hexyl at each occurrence.

[0021] One of the remnants R 1 and R 2 or both remainders R 1 and R 2 can -O -In this case, the compound of general formula I is an anion. The anion of general formula I can form an ionic compound with a cation. The cation is preferably selected from the group consisting of an alkali metal ion, an alkaline earth metal ion, aluminum, iron, and zinc. Therefore, a compound of general formula IB can be provided. (M e b+ ) a (To) (a·b)- (IB), where Me denotes a cation and An a compound of the general formula I, in which R 1 and / or R 2 -O - are, where a is an integer that denotes the number of negative charges of the anion, i.e., 1 or 2, and b is an integer that denotes the number of positive charges of the cation, i.e., 1, 2, or 3.

[0022] R are preferred 1 and R 2independently selected from the group consisting of a substituted or unsubstituted C1-C 12 -alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 12 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylalkyl group and a group -N(R 5 )2, wherein each R 5 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group is present. R is preferred. 1 and R 2 independently selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group and a group -N(R 5 )2, wherein each R 5 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group, consists of. R is particularly preferred.1 and R 2 each independently selected from the group consisting of -N(CH2-CH3)2, phenyl and phenoxy.

[0023] Preferably R 1 and R 2 They have the same meaning. However, they can also have different meanings.

[0024] R 3 and R 4 Together with the nitrogen atom to which they are bonded, they can form a ring or ring system. The ring or ring system can, in addition to the nitrogen atom, include at least one further heteroatom, wherein the further heteroatom is selected from the group consisting of oxygen, nitrogen, and sulfur. Preferably, the additional heteroatom is nitrogen.

[0025] It may be provided that R 3 and R 4 Together with the nitrogen atom, they form a five- or six-membered ring to which no other ring, or one or more rings, are fused. R3 and R 4 Together with the nitrogen atom, a five- or six-membered ring to which one or more rings are fused forms a ring system. This ring system consists of two or more rings. Preferably, the ring system consists of two, three, four, or five rings, more preferably of two or three rings. Each of the rings can contain zero, one, or more heteroatoms, each independently selected from the group consisting of oxygen, nitrogen, and sulfur. Preferably, the fused ring(s) are five- or six-membered. Preferably, two fused rings are provided. The fused rings can be identical or different, preferably they are identical. In one embodiment, R 3 and R 4 Together with the nitrogen atom, it forms a piperidine ring or a pyrrolidine ring. The piperidine ring or the pyrrolidine ring can be substituted or unsubstituted.

[0026] R are preferred 3 and R 4 Selected independently from the group consisting of methyl, ethyl, propyl, butyl, phenyl, and benzyl. R is particularly preferred. 3 and R 4 selected independently from the group consisting of ethyl, phenyl and benzyl.

[0027] Preferably R 3 and R 4 They have the same meaning. However, they can also have different meanings.

[0028] Unless otherwise specified, the term "alkyl" refers in particular to a saturated aliphatic hydrocarbon group having a branched or unbranched carbon chain with 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, octyl, dodecyl, and the like. The alkyl group may optionally be substituted with one or more substituents, each substituent being independently hydroxy, alkyl, alkoxy, amino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino, unless specifically stated otherwise.

[0029] Unless otherwise specified, the term ‘heteroalkyl’ refers in particular to an alkyl group as defined herein, wherein one, two or three hydrogen atoms are replaced by a substituent, independently selected from the group consisting of -OR a , -NR b R c and -S(O) n R d (where n is an integer from 0 to 2), were replaced, provided that the attachment point of the heteroalkyl group is a carbon atom, where R a is hydrogen, acyl, alkyl, cycloalkyl or cycloalkylalkyl; R b and R c are independently hydrogen, acyl, alkyl, cycloalkyl, or cycloalkylalkyl; and when n is 0, R d hydrogen, alkyl, cycloalkyl or cycloalkylalkyl, and if n is 1 or 2, R dAlkyl, cycloalkyl, cycloalkylalkyl, amino, acylamino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino. Representative examples include, but are not limited to, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxy-1-hydroxymethylethyl, 2,3-dihydroxypropyl, 1-hydroxymethylethyl, 3-hydroxybutyl, 2,3-dihydroxybutyl, 2-hydroxy-1-methylpropyl, 2-aminoethyl, 3-aminopropyl, 2-methylsulfonylethyl, aminosulfonylmethyl, aminosulfonylethyl, aminosulfonylpropyl, methylaminosulfonylmethyl, methylaminosulfonylethyl, methylaminosulfonylpropyl, and the like.

[0030] Unless otherwise specified, the term "cycloalkyl" refers in particular to saturated, carbocyclic groups consisting of mono- or bicyclic rings. The cycloalkyl group may optionally be substituted with one or more substituents, each substituent being independently hydroxy, alkyl, alkoxy, amino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino, unless specifically stated otherwise. Examples of cycloalkyl components include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like, including partially unsaturated derivatives thereof, such as cyclohexenyl, cyclopentenyl, and the like.

[0031] Unless otherwise specified, the term "alkenyl" refers in particular to an unsaturated aliphatic hydrocarbon group having a branched or unbranched carbon chain comprising 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms, which has at least one olefinic double bond and more preferably a single double bond. Examples of alkenyl groups include, but are not limited to, vinyl, allyl, methallyl, 1,1-dimethylallyl, propenyl, butenyl, pentadienyl, hexenyl, octenyl, and the like. An allyl group is preferred. The alkenyl group may optionally be substituted with one or more substituents, each substituent being independently hydroxy, alkyl, alkoxy, amino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino, unless specifically stated otherwise.

[0032] Unless otherwise specified, the term "alkynyl" refers in particular to an unsaturated aliphatic hydrocarbon group having a branched or unbranched carbon chain comprising 2 to 18 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and particularly preferably 2 to 6 carbon atoms, which has at least one olefinic triple bond and more preferably a single triple bond. Examples of alkynyl groups include, but are not limited to, acetylenyl, propargyl, n-but-2-yne-1-yl, and the like. A propargyl group is preferred. The alkynyl group may optionally be substituted with one or more substituents, each substituent being independently hydroxy, alkyl, alkoxy, amino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino, unless specifically stated otherwise.

[0033] Unless otherwise specified, the term "alkoxy" refers in particular to a group of the formula -OR, wherein R is an alkyl group, as defined herein. Examples of alkoxy components include, but are not limited to, methoxy, ethoxy, isopropoxy, and the like. The alkoxy group may optionally be substituted with one or more substituents, each substituent being independently hydroxy, alkyl, alkoxy, amino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino, unless specifically stated otherwise.

[0034] Unless otherwise specified, the term "aryl" refers to a cyclic aromatic hydrocarbon group consisting of a mono-, bi-, or tricyclic aromatic ring system with 5 to 18 ring atoms, preferably 5 or 6 ring atoms. The aryl group may optionally be a substituted aryl group. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracyl, naphthalenyl, phenanthryl, fluorenyl, indenyl, pentalenyl, azulenyl, oxydiphenyl, biphenyl, methylenediphenyl, aminodiphenyl, diphenylsulfidyl, diphenylsulfonyl, diphenylisopropylidenyl, benzodioxanyl, benzofuranyl, benzodioxylyl, benzopyranyl, benzoxazinyl, benzoxazinonyl, benzoopiperidinyl, benzoopiperazinyl, benzopyrrolidinyl, benzomorpholinyl, methylenedioxyphenyl, ethylenedioxyphenyl, and the like, including partially hydrogenated derivatives thereof. A preferred example is phenyl.The term “substituted aryl group” refers in particular to an aryl group optionally independently modified with one to four substituents, preferably one or two substituents selected from alkyl, cycloalkyl, heteroalkyl, hydroxyalkyl, nitro, cyano, hydroxy, alkoxy, amino, acylamino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, diarylamino, urea, amido, alkanesulfonyl, -COR (where R is hydrogen, alkyl, phenyl or phenylalkyl), -(CR'R''). n -COOR (where n is an integer from 0 to 5, R' and R'' are independently hydrogen or alkyl, and R is hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl, or phenylalkyl) or -(CR'R'') n -CONR a' R b' (where n is an integer from 0 to 5, R' and R'' are independently hydrogen or alkyl, and R a' and R b'is substituted independently of each other (hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl).

[0035] Unless otherwise specified, the term "heteroaryl" refers in particular to a monocyclic, bicyclic, or tricyclic group with 5 to 18 ring atoms, wherein at least one aromatic ring contains one, two, or three ring heteroatoms selected from N, O, or S, the remaining ring atoms being C. The heteroaryl group may optionally be a substituted heteroaryl group.Beispiele von Heteroaryl-Gruppen umfassen, sind aber nicht beschränkt auf Imidazolyl, Oxazolyl, Isoxazolyl, Thiazolyl, Isothiazolyl, Oxadiazolyl, Thiadiazolyl, Pyrazinyl, Pyridazinyl, Thiophenyl, Furanyl, Pyranyl, Pyridyl, Pyrrolyl, Pyrazolyl, Pyrimidyl, Chinolinyl, Isochinolinyl, Chinazolinyl, Benzofuranyl, Benzothiophenyl, Benzothiopyranyl, Benzimidazolyl, Benzoxazolyl, Benzooxadiazolyl, Benzothiazolyl, Benzothiadiazolyl, Benzopyranyl, Indolyl, Isoindolyl, Indazolyl, Triazolyl, Triazinyl, Chinoxalinyl, Purinyl, Chinazolinyl, Chinolizinyl, Naphthyridinyl, Pteridinyl, Carbazolyl, Azepinyl, Diazepinyl, Acridinyl und dergleichen. Ein bevorzugtes Beispiel ist Pyridinyl.The term “substituted heteroaryl group” refers in particular to a heteroaryl group which may be independently modified with one to four substituents, preferably one or two substituents, selected from alkyl, cycloalkyl, heteroalkyl, hydroxyalkyl, nitro, cyano, hydroxy, alkoxy, amino, acylamino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, diarylamino, urea, amido, alkanesulfonyl, -COR (where R is hydrogen, alkyl, phenyl or phenylalkyl), -(CR'R''). n -COOR (where n is an integer from 0 to 5, R' and R'' are independently hydrogen or alkyl, and R is hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl, or phenylalkyl) or -(CR'R'') n -CONR a' R b' (where n is an integer from 0 to 5, R' and R'' are independently hydrogen or alkyl, and R a' and R b'is substituted independently of each other (hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl).

[0036] Unless otherwise specified, the term ‘acyl’ refers in particular to a group of the formula -C(=O)R, where R is hydrogen or alkyl as defined herein.

[0037] Unless otherwise specified, the term "arylalkyl" refers in particular to a group of the formula -R e R f , where R e an alkylene group and R fan aryl group, as defined herein. The arylalkyl group may optionally be a substituted arylalkyl group. Examples of arylalkyl groups include, but are not limited to, benzyl, phenylethyl, and the like. The term "alkylene" refers in particular to a saturated aliphatic hydrocarbon group having a branched or unbranched carbon chain with 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, and particularly preferably 1 to 6 carbon atoms. Examples of alkylene groups include, but are not limited to, methylene, ethylene, propylene, butylene, and the like. The alkylene group may optionally be substituted with one or more substituents, each substituent being independently hydroxy, alkyl, alkoxy, amino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, or diarylamino, unless specifically stated otherwise.

[0038] Unless otherwise specified, the term "alkylaryl" refers in particular to a group of the formula -R g R h , where R g an aryl group and R h an alkyl group, as defined herein. The alkylaryl group may optionally be a substituted alkylaryl group. Examples of alkylaryl groups include, but are not limited to, o-tolyl, m-tolyl, p-tolyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, and the like.

[0039] Unless otherwise specified, the term "substituted" refers to one or more substituents, each replacing a hydrogen atom of the respective group. The substituent is selected from alkyl, cycloalkyl, heteroalkyl, hydroxyalkyl, nitro, cyano, hydroxy, alkoxy, amino, acylamino, monoalkylamino, dialkylamino, monoarylamino, alkylarylamino, diarylamino, urea, amido, alkanesulfonyl, -COR (where R is hydrogen, alkyl, phenyl, or phenylalkyl), -(CR'R'') n -COOR (where n is an integer from 0 to 5, R' and R'' are independently hydrogen or alkyl, and R is hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl, or phenylalkyl) or -(CR'R'') n -CONR a' R b' (where n is an integer from 0 to 5, R' and R'' are independently hydrogen or alkyl, and R a' and R b'independent of each other are hydrogen, alkyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl).

[0040] Preferred compounds of general formula I are shown in Table 1. The "Formula" column shows, with the exception of compound PB-175, the compound in two different representations, with the lower representation showing the R groups bonded to the phosphorus atom. 1 and R 2 and the R groups bonded to the nitrogen atom of the compound of general formula I 3 and R 4 Each is grouped together in parentheses. The meanings of the two representations do not differ. Table 1 Designation formula name PB-163 N,N-Dibenzylcarbamoyloxydiphenoxyphosphine oxide PB-165 N,N-Dibenzylcarbamoyloxydiphenylphosphine oxide PB-167 N,N-Diethylcarbamoyl-oxydiphenoxyphosphine oxide PB-175 10-(N,N-Diethylcarba-moyloxy)-9,10-dihydro-9-oxa-10-phosphaphenane-tren-10-oxide PB-179 10-(N,N-Dibenzylcarba-moyloxy)-9, 10-dihydro-9-oxa-10-phosphaphenane-tren-10-oxide

[0041] The following describes processes for the preparation of compounds of general formula I and processes for the preparation of compounds that can be used as precursors. Unless otherwise stated, the term "equivalents" refers to molar fractions of the reacting substance.

[0042] The product normally occurs in its pure form. Unless otherwise specified, the purification of the reaction products can be carried out as follows: Impurities can be removed without a protective gas by washing a solution in an aprotic, water-insoluble solvent, e.g., chloroform, dichloromethane, or ethyl acetate, with saturated sodium bicarbonate solution, water, and dilute (approx. 5%) HCl. The organic phase is then dried with a suitable drying agent. Drying can be carried out, for example, with sodium sulfate or 3 Å molecular sieve. It should not be carried out with magnesium or calcium salts, metal hydrides, or alkali and alkaline earth metals. Alternatively, the compounds can be purified, optionally under a protective gas, by recrystallization, extraction with nonpolar aprotic solvents, or partial distillation / sublimation.

[0043] In contrast to Munoz's syntheses, which were only carried out on a milligram scale and are difficult to scale up, the described procedures have already been performed with quantities exceeding 10 g. Due to the optimized reaction conditions and, if necessary, simple work-up, easy scale-up is readily achievable. The phosphoryl chlorides and phosphoryl bromides used preferentially, especially the phosphoryl chlorides, are non-explosive. Toxic and explosive azides are not released during the reaction and work-up. First method according to the invention

[0044] According to the invention, a first method for producing a compound of general formula I is provided, which involves the reaction of a compound of general formula II in R 1 , R 2 , R 3 and R 4which have meanings given in connection with the general formula I, with oxygen or an oxygen-containing oxidizing agent to form a compound of general formula I.

[0045] The compound of general formula II is a trivalent phosphorus carbamate. The first process according to the invention is illustrated in Scheme 1:

[0046] If the oxidizing agent is oxygen, it is preferably molecular oxygen (O₂). The oxygen-containing oxidizing agent can be selected, for example, from the group consisting of molecular oxygen (O₂), hydrogen peroxide, potassium permanganate, organic peroxides, hypochlorides, chlorates, and non-nucleophilic hydroperoxides. An example of a non-nucleophilic hydroperoxide is tert-butyl hydroperoxide. A preferred oxygen-containing oxidizing agent is hydrogen peroxide.

[0047] In contrast to the oxidation of trivalent phosphorus carbamates with sulfur to N,N-disubstituted thiophosphoryl carbamates, the oxidation of trivalent phosphorus carbamates with an oxygen-containing oxidizing agent to obtain the N,N-disubstituted phosphoryl carbamates exhibits higher chemical reactivity. The thermal decomposition behavior also differs between the sulfur compounds and the compounds of general formula I. Due to their different thermal stability and chemical reactivity, the compounds of general formula I are better suited as flame retardants compared to N,N-disubstituted thiophosphoryl carbamates.

[0048] An embodiment of the first process according to the invention, in which molecular oxygen (O2) is used as an oxidizing agent, and an embodiment of the first process according to the invention, in which an oxygen-containing oxidizing agent is used, are explained below. a) Use of molecular oxygen (O2)

[0049] This embodiment is preferably carried out in a nonpolar aprotic solvent, for example hexane, pentane, heptane, or dibutyl ether. The solvent should be dry. The concentration of the compound of general formula II in the solvent is not particularly limited. For example, the compound of general formula II can be provided as a 0.05 to 2 M solution.

[0050] The compound of general formula II can be reacted with an excess of oxygen (O₂). Alternatively, oxygen can be added until the solution of the compound of general formula II is saturated. Preferably, the process is carried out at room temperature, for example, at 15 to 25 °C. The process can be carried out at a pressure of 1 to 10 bar (100 to 1000 kPa). It can be carried out at ambient pressure, for example, 101.325 kPa. The process can be carried out for a period of 1 to 30 days. Preferably, the process is carried out with agitation, for example, stirring. The reaction can be carried out under a protective gas, for example, argon or nitrogen.

[0051] In one example of this embodiment of the first process according to the invention, the procedure is as follows: Under a protective gas, e.g., argon or nitrogen, a solution, e.g., a 0.05 to 2 M solution, of a compound of general formula II in a dry, preferably nonpolar aprotic solvent, e.g., hexane, pentane, heptane, or dibutyl ether, is stirred under a pressure of 1 to 10 bar (100 to 1000 kPa) for 1 to 30 days. The solvent is then removed under vacuum. The target compound, i.e., a compound of general formula I, is normally obtained in a pure form. However, it can also be subjected to purification. b) Use of an oxygen-containing oxidizing agent

[0052] This embodiment is preferably carried out in a polar aprotic solvent, for example in tetrahydrofuran (THF), dimethyl ether (DME), dimethyl carbonate (DMC), or nitromethane. The concentration of the compound of general formula II in the solvent is not particularly limited. For example, the compound of general formula II can be provided as a 0.03 M solution.

[0053] The oxygen-containing oxidizing agent can be used in excess of the compound of general formula II. The compound of general formula II and the oxygen-containing oxidizing agent can be reacted in a molar ratio, based on the reacting functional groups, of 1:1 to 2, preferably 1:1. The process can be carried out at a temperature of 0 to 25 °C, with a temperature of 0 to 10 °C being preferred. The process can be carried out at ambient pressure, for example 101.325 kPa.

[0054] In an example of this embodiment of the first process according to the invention, the procedure is as follows: To a solution, which may be, for example, a 0.3 M solution, of one equivalent of the compound of general formula II in a polar aprotic solvent, e.g., THF, DME, DMC, or nitromethane, one equivalent of the oxygen-containing oxidizing agent is added at 0 °C. The oxygen-containing oxidizing agent may be dissolved in a polar aprotic or polar protic solvent, preferably in a polar aprotic solvent, but this is not necessary. In the case of hydrogen peroxide, hydrogen peroxide can be used as a 1% or higher percentage aqueous solution, for example, as a 30% solution. It is allowed to warm to room temperature and stirred for 0 to 4 hours. For work-up, all volatile components are removed from the target compound, i.e.,The compound of general formula I is separated under vacuum. Preferably, the target compound is not heated in aqueous solution.

[0055] The process can be carried out under a protective gas, for example nitrogen or argon. This is particularly advantageous if the target compound is prone to hydrolysis. In this case, the use of a dry aprotic solvent is also preferred. Furthermore, an aprotic oxidizing agent, e.g. potassium permanganate, hypochlorides, or chlorates, should be used. Second method according to the invention

[0056] According to the invention, a second inventive method for producing a compound of general formula I is further provided, which involves the reaction of a compound of general formula III wherein R 1 and R 2which have meanings given in connection with general formula I; and X Chlorine or bromine is; with a compound of general formula IV or a compound of general formula V wherein in the general formula IV R 3 and R 4 the meanings given in connection with general formula I and Z is selected from the group consisting of an alkali metal, an alkaline earth metal, aluminium, iron, zinc or a group -Si(R 6 )3 consists of which R 6 regardless of whether a substituted or unsubstituted C1-C cell occurs in each instance 18 -Alkyl group is; in the general formula VR 3 and R 4 which have meanings given in connection with the general formula I; to a compound of the general formula I.

[0057] In the compound of general formula III, X is preferably chlorine. The compound of general formula III is a phosphoryl halide. Phosphoryl halides are significantly more reactive, cheaper, and easier to handle than the phosphoryl azides used by Munoz et al. For this reason, the syntheses and reaction conditions of Munoz et al. cannot be transferred to phosphoryl halides. The second process according to the invention does not use a phosphoryl azide.

[0058] An embodiment of the second method according to the invention, in which the compound of general formula IV is used, and an embodiment of the second method according to the invention, in which the compound of general formula V is used, are explained below. a) Use of the compound of general formula IV

[0059] The compound of general formula IV is a metal or semimetal carbamate. The second method according to the invention, using a compound of general formula IV, is illustrated in Scheme 2:

[0060] In addition to the compound of general formula I, metal or metalloid chlorides can be formed during the reaction, for example LiCl or Si(R 6 )3Cl.

[0061] In the compound of general formula IV, Z is preferably lithium or -Si(R) 6 )3, wherein R 6 regardless of whether a substituted or unsubstituted C1-C cell occurs in each instance 18 -alkyl group is preferred. 6 a substituted or unsubstituted C1-C 12 -Alkyl group, more preferably a substituted or unsubstituted C1-C6 alkyl group, and even more preferably methyl, ethyl, propyl, butyl, pentyl, or hexyl, and particularly preferably methyl. The R groups 6They can have the same or different meanings. Preferably, they have the same meaning. All three residues R are especially preferred. 6 Methyl.

[0062] The procedure can be carried out without the use of a solvent. This is particularly advantageous if the compound of general formula IV is liquid. Alternatively, the procedure can be carried out in a polar aprotic solvent, for example, tetrahydrofuran (THF) or another ether, chloroform, dichloromethane, nitromethane, or phosphoric acid esters or amides. The solvent should be dry. The concentration of the compound of general formula IV in the solvent is not particularly limited. For example, the compound of general formula IV can be provided as a 0.05 to 2 M solution.

[0063] The compound of general formula III can be provided without a solvent. However, it can also be provided in a polar aprotic solvent, for example, in tetrahydrofuran (THF) or another ether, chloroform, dichloromethane, nitromethane, or phosphoric acid esters or amides. Preferably, it is provided in the same manner as the compound of general formula IV, i.e., without a solvent if the compound of general formula IV is used without a solvent, or in the polar aprotic solvent—preferably in the same polar aprotic solvent—if the compound of general formula IV is provided in a solvent. The concentration of the compound of general formula III in the solvent is not particularly limited. For example, the compound of general formula III can be provided as a 0.05 to 2 M solution.

[0064] The compound of general formula III and the compound of general formula IV can be reacted in a molar ratio of 1:1 to 4, preferably 1:1 to 2. The compound of general formula III and the compound of general formula IV can be brought into contact with each other at a temperature of -20 °C to room temperature. The reaction can then be carried out at room temperature. The reaction can be carried out for a period of 30 minutes to three months with agitation, for example, stirring. The process can be carried out at ambient pressure, for example, 101.325 kPa. The process can be carried out under a protective gas, for example, nitrogen or argon.

[0065] In one example of this embodiment of the second process according to the invention, the procedure is as follows: Under a protective gas atmosphere, one to two equivalents of the compound of general formula IV are added dropwise to one to two equivalents of the compound of general formula IV without solvent, if the metal carbamate is a liquid metal carbamate, or with a suitable dry polar aprotic solvent, for example THF or another ether, chloroform, dichloromethane, nitromethane, or a phosphoric acid ester or amide, at -20 °C to room temperature. The mixture is then stirred at room temperature for half an hour to three months. For isolation, the resulting metal or semimetal chloride is separated by filtration or distillation under vacuum. Subsequently, all (other) volatile components are separated by distillation under vacuum. The target compound, i.e.,The compound of general formula I can, if necessary, be subjected to purification. b) Use of the combination of the general formula V

[0066] The compound of general formula V is a secondary amine. The second method according to the invention using a compound of general formula V is illustrated in Scheme 3:

[0067] The reaction of the compound of general formula III with the compound of general formula V and carbon dioxide takes place in the presence of an auxiliary base. In addition to the compound of general formula III, the reaction may yield ammonium chloride if X in the compound of general formula III is chlorine, or ammonium bromide if X is bromine. This is the chloride or bromide salt of the ammonium cation, which arises from the intermediately formed ammonium carbamate.

[0068] The auxiliary base can be, for example, an amine. The amine can be selected, for instance, from the group consisting of triethylamine, substituted guanidines, diazabicycloundecene (DBU), 1,5-diazabicyclo(4,3,0)non-5-ene (DBN), diisopropylethylamine, 1,8-bis(N,N-dimethylamino)naphthalene, and diisopropylamine.

[0069] The process is preferably carried out in a polar aprotic solvent, for example, tetrahydrofuran (THF), dichloromethane, or acetonitrile. Preferably, the compound of general formula V and the auxiliary base are provided in one to ten times the volume of the solvent. The solvent should not freeze at the reaction temperature. The solvent is preferably dry. It may be provided that 1 to 2 equivalents of the compound of general formula V are provided with one equivalent of the auxiliary base. The use of 1 equivalent of the compound of general formula V is advantageous if the work-up procedure B described in the "Examples" section is chosen.

[0070] CO₂ can be added to the solution of the compound of general formula V and the auxiliary base at ambient pressure, for example 101.325 kPa, or at an overpressure. For example, CO₂ can be added at a pressure of 1 to 8 bar (100 kPa to 800 kPa). Preferably, CO₂ is added until the saturation limit of the solution is reached. The reaction can be carried out with agitation, for example stirring, for a period of 1 to 24 hours. The CO₂ can be added at ambient temperature.

[0071] After the CO2 supply is complete, preferably after reaching the saturation limit, the reaction mixture can be cooled to a temperature of -78 °C to 0 °C, preferably -78 °C to -41 °C. Subsequently, the compound of general formula III can be introduced into the reaction mixture. The compound of general formula III can be provided in a polar aprotic solvent. Preferably, it is provided in the same solvent as the compound of general formula V and the auxiliary base. For example, the compound of general formula III can be provided as a 0.005 to 1 M solution.

[0072] The process can be carried out under a protective gas, for example nitrogen or argon.

[0073] In one example of this embodiment of the second process according to the invention, the procedure is as follows: Under a protective gas atmosphere, 1 to 2 equivalents of the compound of general formula V are dissolved with 1 to 2 equivalents of the auxiliary base in one to ten times the volume of the dry polar aprotic solvent, for example, THF, dichloromethane, or acetonitrile. The use of only 1 equivalent of the compound of general formula V is advantageous if work-up procedure B, described in Section 2 “Examples,” is selected. The equivalents given refer to 1 equivalent of the phosphoryl halide added subsequently. The solvent must not freeze at the cooling temperature. The solution is then stirred with CO₂ at 1 to 8 bar (100 kPa to 800 kPa) for 1 to 24 hours until saturation is reached.The solution is used without further dilution or after dilution to a maximum of three times its volume with the same solvent. It is then cooled to -78 °C to 0 °C, and the phosphoryl halide is slowly added dropwise in the same solvent as a 0.05 to 1 M solution. Work-up is carried out in an inert or aqueous manner, depending on the sensitivity of the target compound, i.e., the compound of general formula I. The precipitated ammonium halide is filtered off. To ensure complete precipitation, a suitable (optionally dry, if using an inert work-up) nonpolar solvent, such as ethyl acetate, toluene, or benzene, may be added beforehand. Further work-up procedures are described in the general purification procedure given above. Third method according to the invention

[0074] The third process according to the invention enables the preparation of a precursor that can be used for the preparation of a compound of general formula I. The third process according to the invention is directed towards the preparation of a compound of general formula XI from a compound of general formula XII (see Scheme 4). The compound of general formula II is a trivalent phosphorus halide. Trivalent phosphorus halides are also known as halophosphanes.

[0075] The compound of general formula IV has already been described in connection with the second method according to the invention. Reference is made to that description. In the compound of general formula IV, Z is preferably -Si(R 6 )3.

[0076] In the combination of general formula XII, X Chlorine or bromine, preferably chlorine, and R 7 and R 8are independently selected from the group consisting of hydrogen, bromine, chlorine, a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 18 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -N(R 9 )2 and -OC(O)N(R 9 )2 consists of which each R 9 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group or a substituted or unsubstituted aryl group.

[0077] R are preferred7 and R 8 independently selected from the group consisting of bromine, chlorine, a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 18 -alkoxy group and a substituted or unsubstituted aryloxy group. Preferably R 7 and R 8 independently of each other, either chlorine or a substituted or unsubstituted aryl group.

[0078] The ones related to R 7 and R 8 mentioned substituted or unsubstituted C1-C 18 The -alkyl group is preferably either a substituted or unsubstituted C1-C 12 -Alkyl group, more preferably a substituted or unsubstituted C1-C6 alkyl group and particularly preferably methyl, ethyl, propyl, butyl, pentyl or hexyl.

[0079] The ones related to R 7 and R8 mentioned substituted or unsubstituted C2-C 18 The -alkenyl group is preferably either a substituted or unsubstituted C2-C 12 -Alkenyl group, more preferably a substituted or unsubstituted C2-C6 alkenyl group and particularly preferably ethenyl, propenyl, butenyl, pentenyl or hexenyl.

[0080] The ones related to R 7 and R 8 mentioned substituted or unsubstituted C2-C 18 The -alkynyl group is preferably either a substituted or unsubstituted C2-C 12 -Alkynyl group, more preferably a substituted or unsubstituted C2-C6 alkynyl group and particularly preferably ethinyl, propynyl, butynyl, pentinyl or hexinyl.

[0081] In connection with R 7 and R 8 is a group -N(R 9 )2 provided, wherein each R 9 independently of each other, one substituted or unsubstituted C1-C 12-alkyl group or a substituted or unsubstituted aryl group. The two R groups 9 They can be the same or different. The remainder R is preferred. 9 Each occurrence is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl.

[0082] In connection with R 7 and R 8 is a group -OC(O)N(R 9 )2 provided, wherein each R 9 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group or a substituted or unsubstituted aryl group. The two R groups 9 They can be the same or different. The remainder R is preferred. 9 Each occurrence is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl.

[0083] Preferably R 7 and R 8They have the same meaning. However, they can also have different meanings.

[0084] In the combination of the general formula XI, R 3 and R 4 the meanings given in connection with general formula I. In addition to the compound of general formula XI, a metal or semimetal chloride is formed, for example Si(R) 6 )3Cl. In addition, CO2 can be produced in some cases.

[0085] The third process according to the invention enables the preparation of carbamoyloxyphosphanes, i.e., the compounds of general formula XI, from carbamoyloxysilanes, i.e., the compounds of general formula IV. The third process according to the invention can be used independently of the preparation of compounds of general formula I.

[0086] The procedure can be carried out in an aprotic solvent, for example, tetrahydrofuran (THF), chloroform, dichloromethane, or diethyl ether. A solvent is not required if the compound of general formula IV and the compound of general formula XII are both liquid. The concentration of the compound of general formula IV in the solvent is not particularly limited. For example, the compound of general formula IV can be provided as a 0.05 to 2 M solution.

[0087] The compound of general formula IV and the compound of general formula XII can be reacted in a molar ratio of 1 to 4:1. The compound of general formula XII and the compound of general formula IV can be brought into contact at temperatures ranging from -41 °C to room temperature. In a first variant, the reaction can then be carried out at room temperature for a period of 1 hour to 1 month with agitation, for example, by stirring. Alternatively, in a second variant, the reaction can be carried out for 1 to 6 hours at 34 °C to 150 °C with agitation, for example, by stirring, optionally removing volatile metal or semimetal halide by distillation. Distillational separation of the byproducts is possible if Z-Si(R) 6)3. The process can be carried out at ambient pressure, for example 101.325 kPa. The process can be carried out under a protective gas, for example nitrogen or argon. The purification of the crude product can be carried out under a protective gas by vacuum distillation or by recrystallization.

[0088] In an example of the third process according to the invention, the procedure is as follows: Under a protective gas atmosphere, 1 to 4 equivalents of the compound of general formula IV are placed in a suitable dry aprotic solvent. However, a solvent is not necessary if the compound of general formula IV and the trivalent phosphorus halide, i.e., the compound of general formula XII, are liquid. The solvent is, for example, THF, chloroform, dichloromethane, or diethyl ether. Subsequently, at -41 °C to room temperature, one equivalent of the trivalent phosphorus halide is added dropwise. Then, the mixture is stirred at room temperature for one hour to one month, or it is heated at 34 °C to 150 °C for one to six hours, optionally removing volatile metal chloride by distillation, which is possible if Z-Si(R) 6)3. If any metal or semimetal halide formed has precipitated, it is filtered off. Subsequently, all volatile components are removed under vacuum, and the product, i.e., the compound of general formula XI, is purified either by distillation or by recrystallization.

[0089] According to the invention, a product is further provided which contains at least one polymer. The product comprises a flame retardant, wherein the flame retardant is a compound of general formula I.

[0090] The product according to the invention can contain a polymer or a mixture of two or more polymers. The product according to the invention can consist of the polymer or the mixture of two or more polymers on the one hand and the flame retardant on the other. The polymer can be a homopolymer or a copolymer. The product according to the invention can be a thermoplastic, a thermoset, or a vitrimer. The compound of general formula I can thus be used as a flame retardant for thermoplastics, thermosets, and vitrimers. Examples of polymers include polystyrene (PS) and polylactic acid (PLA). Polylactic acid is also known as polylactide. The effect of the flame retardants according to the invention is not limited to specific polymers, such as certain rigid foams.

[0091] To produce the product according to the invention, the compound of general formula I can be mixed with the polymer during the polymer's production or processing, or it can be bonded to the polymer by covalent bonds. The polymer can be processed, for example, in an extruder. The weight fraction of the compound of general formula I in the product according to the invention depends on the specific polymer. Depending on the type of polymer, small or large weight fractions of the compound of general formula I may be required. The weight fraction of the compound of general formula I can therefore range from 1 to less than 50 wt.%, preferably 1 to 40 wt.%, in each case based on the sum of the weight of the polymer(s) and the weight of the flame retardant.

[0092] The product according to the invention can be a mixture of at least one polymer and a compound of general formula I. The weight fraction of the compound of general formula I can in this case be in the range of 1 to less than 50 wt.%, preferably 1 to 40 wt.%, in each case based on the weight of the mixture.

[0093] The processes according to the invention allow for the recycling of particularly expensive compounds. In some cases, CO2 is used as a building block for synthesis. It is therefore possible to use the produced compounds as CO2 storage. All process steps can be scaled up to industrial levels and are relatively energy-efficient. Column chromatography for the purification of the compounds of general formula I is not required. The compounds of general formula I all exhibit flame-retardant properties.

[0094] The invention is explained in more detail below with reference to exemplary embodiments which are not intended to limit the invention. Examples

[0095] As the following examples show, in one embodiment of the invention, a process is provided that starts with aminosilanes, which are readily produced in very good yields, and enables the synthesis of silyl carbamates (also known as carbamoyloxysilanes) by CO2 insertion. This CO2 insertion also proceeds very well solvent-free at room temperature in very good yields. The resulting silyl carbamates can, in turn, be reacted with readily available phosphorus halide compounds to form a little-known and scarcely investigated class of substances, the carbamoyloxyphosphine oxides. Likewise, the new flame retardants can be generated by the insertion of CO2 into PN bonds of suitable starting materials.Surprisingly, this class of compounds now shows very promising results in "Limiting Oxygen Index Tests" (LOI tests) in the polymer materials polystyrene (PS) and polylactic acid (PLA), indicating high effectiveness as flame retardants.

[0096] Abbreviations used in the examples: Bn Benzyl Et Ethyl Ph Phenyl THF Tetrahydrofuran Examples 1 to 5

[0097] Examples 1 to 5 illustrate the preparation of compounds that can be used to synthesize compounds of general formula I. Example 1 illustrates the synthesis of phosphoryl chlorides. Examples 2 and 3 illustrate the synthesis of metal carbamates. Examples 4 and 5 illustrate the synthesis of aminophosphanes and their reactions with CO2. Example 1 Synthesis of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide 2

[0098] Scheme B-1 illustrates the preparation of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 2 by chlorination of 9,10-dihydro-9-oxa-10-phos-pha-phenanthrene-10-oxide 1 (DOPO).

[0099] The procedure is known from

[16] . 50 g (0.231 mol) of DOPO were dissolved in approximately 125 ml of dry dichloromethane and cooled to 0 °C. Chlorine gas was then introduced until the solution turned yellow and no longer decolorized. Subsequently, all volatile components were removed under vacuum by condensation in a cold trap. 57.936 g of compound 2 were obtained as a white solid (quantitative yield). m = 89 °C.

[0100] NMR data for compound 2: 31 P-NMR: (162 MHz, CDCl3) δ = 20.0 (P 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) δ = 149.1 (d, C 1 , J C1-P = 9.7 Hz), 136.0 (d, C 3 , J C3-P = 8.5 Hz), 134.7 (d, C 4, J C4-P = 2.8 Hz), 131.2 (d, C 6 , J C5-P = 10.6 Hz), 131.1 (C 5 ), 128.9 (d, C 7 , J C7-P = 16.9 Hz), 125.9 (C 8 ), 125.4 (C 9 , J C9-P = 1.8 Hz), 125.3 (d, C 12 , J C12-P = 164.6 Hz), 124.5 (d, C 10 , J C10-P = 13.1 Hz), 122.2 (d, C 11 , J C11-P = 13.5 Hz), 120.6 (d, C 13 , J C13-P = 7.4 Hz)ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 8.07 (dddd, 1H, H(C 9 )), 8.00 (t, 1H, C 7 ) 7.96 (dd, 1H, H(C 4 )), 7.79 (tt, 1H, H(C 3 )), 7.59 (tdd, 1H, H(C 6 )) 7.47 (ddt, 1H, H(C 5 )) 7.37 (ddt, 1H, H( C8 )), 7.30 (m, 1H, H(C 12 )) ppm. Example 2 Synthesis of diethylcarbamoyloxytrimethylsilane 4

[0101] Diethylcarbamoyloxytrimethylsilane 4 was prepared according to the procedure shown in Scheme B-2.

[0102] Carbon dioxide was introduced into 10 g of freshly distilled diethylaminotrimethylsilane 3 under ice-cooled, solvent-free conditions for 90 minutes. The reaction was quantitative.

[0103] NMR and IR data for compound 4: 29 Si-INEPT NMR: (99 MHz, CDCl3) δ=21.9 (Si 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) δ = 154.8 (C 1 ), 41.9 (C 2 ), 41.3 (C 3 ), 14.0 (C 4 ), 13.4 (C 5 ), 0.0 (C 6 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 3.10 (m, 4H, H(C 2 +C 3 )), 0.95 (q, 6H, H(C 4 +C 5 )), 0.12 (s, 9H, H(C 6 )) ppm. The multiplet at 3.10 ppm in the ¹H NMR spectrum consists of the two not fully resolved quartet signals of the cis and trans CH₂ groups. IR: (ATR) v = 611.4 (vw), 626.8 (vw), 663.4 (vw), 694.3 (vw), 711.6 (vw), 742.5 (w), 781.1 (w), 813.9 (w), 842.8 (vs, v Si-C / τ CH₃

[17] ), 939.2 (vw), 972.0 (w), 1062.6 (w), 1087.7 ​​(vw), 1097.4 (vw), 1178.4 (m), 1228.5 (vw), 1249.7 (m, CH3-Si δ

[18] ), 1278.6 (m, CO-Si v

[18] ). 2971.9 (vw) cm -1 . Example 3 Synthesis of lithium N-methyl N-phenylcarbamate 6

[0104] Lithium N-methyl N-phenylcarbamate 6 was prepared according to the procedure shown in Scheme B-3.

[0105] 25 g of lithium N-methyl-N-phenylamide 5 were suspended in 200 ml of tetrahydrofuran (THF) and treated with carbon dioxide for 12 h under ice-cooled conditions. Amide 5 initially dissolved with a significant release of heat, and after a few minutes the product carbamate (compound 6) precipitated out. The completeness of the reaction was verified by checking whether the supernatant solution became cloudy again upon further treatment. Finally, the solvent was removed under vacuum by condensation in a cold trap. The reaction proceeded quantitatively. Product 6 was obtained as a white solid. m = 231 °C (decomposition).

[0106] NMR and IR data for compound 6: 13C -NMR: (101 MHz, THF-d8) δ = 151.2 (C 1 ), 129.7 (C 2 ), 116.9 (C 3 ), 113.6 (C 4 ), 30.7 (C 5 ) ppm. 1 H-NMR: (500 MHz, THF-d8) δ = 7.03 (m, 2H, H(C 2 )), 6.51 (m, 2H, H(C4 )), 6.49 (s, 1H, H(C 3 )), 2.74 (s, 1.5 H, H(C 5 )), 2.73 (s, 1.5 H, H(C 5 )) ppm. IR: (ATR) v = 632.6 (vs, δCN

[20] ), 651.9 (m), 692.4 (vs, δCNC

[20] ), 757.9 (m), 804.2 (s, out of plane δ 5 Ar-H

[20] ), 846.6 (vw), 898.7 (w, out of plane δ 5 Ar-H

[20] ), 981.6 (w), 1000.9 (w), 1027.9 (w), 1074.2 (w), 1105.1 (s), 1153.3 (w), 1178.4 (w), 1201.5 (m), 1301.8 (vs), 1355.8 (vs), 1394.4 (m), 1436.8 (vs), 1458.0 (s), 1492.7 (s, v C=O

[19] ), 1521.6 (m), 1571.8 (m), 1600.7 (s, v C=O

[19] ), 2811.8 (vw), 2914.0 (vw), 3027.8 (vw), 3054.8 (vw), 3413.5 (vw) cm -1 . Example 4 Synthesis of Tris(diethylamino)phosphine 8

[0107] Scheme B-4 illustrates the preparation of tris(diethylamino)phosphine 8 from diethylamine 7. Here, the abbreviation "Et" denotes an ethyl group.

[0108] Into a solution of 27.580 g (0.377 mol) of diethylamine 7 in approximately 200 ml of diethyl ether, 8.200 g (0.060 mol) of phosphorus trichloride in approximately 50 ml of diethyl ether were slowly added dropwise at 0 °C with vigorous stirring. The suspension was allowed to warm to room temperature and stirred overnight. The suspension was then filtered, and the solvent was separated by condensation in a cold trap under vacuum. The crude product was then treated with approximately 50 ml of hexane, and the remaining precipitated hydrochloride was filtered off. The solvent was again separated by condensation in a cold trap under vacuum. Finally, 9.300 g of product 8 (63.0%) were obtained as a colorless, extremely oxidation-sensitive liquid.

[0109] NMR data for compound 8 31 P-NMR: (162 MHz, C6D6) δ = 118.8 (P 1 ) ppm. 13 C-NMR: (101 MHz, C6D6) δ = 39.7 (d, C 1 , J C1-P = 19.8 Hz), 14.3 (d, C 2 , J C1-P= 3.0 Hz) ppm. 1 H-NMR: (500 MHz, C6D6) δ = 2.96 (dq, 12H, H(C 1 ), J H(C1)-P = 8.5 Hz, J H(C1)-H(C2) = 7.1 Hz), 1.03 (t, 18H, H(C 2 ), J H(C1)-H(C2) = 7.1 Hz) ppm. Example 5 Synthesis of bis(diethylamino)diethylcarbamoyloxyphosphane 9 and diethylaminobis(diethylcarbamoyloxy)phosphane 10

[0110] Scheme B-5 illustrates the reaction of tris(diethylamino)phosphine, prepared as described in Example 4, with CO2 to give bis(diethylamino)diethylcarbamoyloxyphosphine 9 and diethylaminobis(diethylcarbamoyloxy)phosphine 10. The abbreviation “ex. CO2” means that CO2 was used in excess.

[0111] 9,300 g of Tris(diethylamino)phosphine 8 were treated with CO2 injection under stirring for 2.5 h. The mixture was then distilled under vacuum. The following yields were obtained: Diethylaminobis(diethylcarbamoyloxy)phosphine 10 (diinsertion product) 11.7%, Bis(diethylamino)diethylcarbamoyloxyphosphine 9 (monoinsertion product) 78.3%, and Tris(diethylamino)phosphine 8 (starting material) 6.6% (the remainder was lost due to oxidation with oxygen).

[0112] As an alternative to vacuum distillation, the reaction mixture obtained by introducing CO2 into tris(diethylamine)phosphine 8 was stirred for one hour in an autoclave at 4 bar (400 kPa) CO2. After distillation, the following yields were obtained: 28.5% diethylaminobis(diethylcarbamoyloxy)phosphine 10 and 66.7% bis(diethylamino)diethylcarbamoyloxyphosphine 9.

[0113] NMR and IR data for bis(diethylamino)diethylcarbamoyloxyphosphine 9: 31 P-NMR: (162 MHz, C6D6) δ = 123.6 (P 1 ) ppm.13 C-NMR: (126 MHz, C6D6) δ = 154,1 (d, C 1 , J C1-P = 7,3 Hz), 41,8 (C 2 ), 41,7 (C 3 ), 40,2 (d, C 4 , J C4-P = 20,2 Hz), 14,9 (C 5 ), 13,7 (C 6 ), 13,2 (C 7 ) ppm. 1 H-NMR: (500 MHz, C6D6) δ = 3,16 (m, 8H, H(C 4 )), 2,96 (m, 4H, H(C 2 +C 3 )) 0,87-1,17 (m, 18H, H(C 5 -C 7 )) ppm. IR: (ATR) v = 630,6 (s, v sym PNC

[20] ), 671,1 (w), 923,8 (w, v P-O

[20] ), 964,3 (w), 1010,6 (w), 1053,0 (w, v as PNC

[20] ), 1122,4 (m), 1166,8 (s, v C-O in COP

[20] ), 1249,7 (w), 1274,8 (s, v C-O in COP

[20] ), 1377,0 (m), 1415,6 (s), 1471,5 (m), 1679,8 (vs, v C=O), 2966,1 (s, v NCH

[20] )

[0114] NMR- und IR-Daten für Diethylaminobis(diethylcarbamoyloxy)phosphan 10: 31 P-NMR: (162 MHz, C6D6) δ = 129,7 (P 1 ) ppm. 13C-NMR: (126 MHz, C6D6) δ = 154,8 (d, C 1 , J C1-P = 8,7 Hz), 42,4 (C 2 ), 42,0 (C 3 ), 39,5 (d, C 4 , J C4-P = 23,3 Hz), 15,0 (d, C 5 , J C5-P = 3,9 Hz), 14,6 (C 6 ), 13,8 (C 7 ) ppm. 1 H-NMR: (500 MHz, C6D6) δ = 3,15 (m, 8H, H(C 2 +C 3 )), 3,04 (q, 4H, H(C 4 ), J H(C4)-H(C5) = 7,1 Hz), 1,04 (t, 6H, H(C 5 ), J H(C4)-H(C5) = 7,1 Hz), 0,98 (t, 6H, H(C 6 )), 0,95 (t, 6H, H(C 7 )) ppm. IR: (ATR) v = 632,6 (m, v sym PNC

[20] ), 675,0 (m), 727,1 (m), 790,7 (w), 937,3 (m, v P-O

[20] ), 956,6 (m), 1024,1 (s, v as PNC

[20] ), 1155,2 (vs, v C-O in COP

[20] ), 1224,6 (m), 1267,1 (vs, v C-O in COP

[20] ), 1378,9 (s), 1417,5 (s), 1471,5 (m), 1679,8 (vs, C=O), 2279,6 (w), 2970,0 (m, v NCH

[20] ) cm -1 . Beispiele 6 und 7

[0115] Examples 6 and 7 illustrate the synthesis of carbamoyloxyphosphanes from carbamoyloxysilanes. Example 6 Synthesis of Diethylaminobis(diethylcarbamoyloxy)phosphine 10

[0116] In an alternative synthesis route to Example 5, diethylaminobis(diethylcarbamoyloxy)phosphine 10 was prepared by reacting diethylcarbamoyloxytrimethylsilane 4 with PCl3 according to the procedure shown in Scheme B-6. Diethylcarbamoyloxytrimethylsilane 4 was prepared as described in Example 2.

[0117] Under ice-cooled conditions and vigorous stirring, 3.573 g (26.017 mmol) of phosphorus trichloride were slowly added dropwise to 17.619 g (93.060 mol) of diethylcarbamoyloxytrimethylsilane 4 in approximately 10 ml of chloroform. The mixture was then heated under reflux for one hour. Subsequently, an NMR sample was taken, and all volatile components were separated by condensation in a cold trap under vacuum. The residue was then distilled under vacuum at a boiling point of 110 °C and a pressure of 8.80 mL. -3 Product 10 was distilled off at mbar. 4.150 g (47.6% yield based on phosphorus trichloride) of diethylaminobis(diethylcarbamoyloxy)phosphine 10 was obtained as a colorless liquid.

[0118] NMR data for compound 10 31 P-NMR: (162 MHz, CDCl3) δ = 127.1 (s, P 1 ) ppm. 13 C-NMR: (126 MHz, CDCl3) δ = 153.7 (d, C 1 , J C1-P = 8.9 Hz), 42.1 (C 2 ), 41.7 (C 3 ), 39.0 (d, C 4 , JC4-P = 23.3 Hz), 14.7 (d, C 5 , J C5-P = 3.9 Hz), 14.1 (C 6 ), 13.4 (C 7 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 3.28 (m, 8H, H(C 2 +C 3 )), 3.18 (q, 4H, H(C 4 )), 1.13 (m, 18H, H(C 5 -C 7 )) ppm.

[0119] In an alternative method, the phosphorus trichloride was added dropwise at room temperature – the flask was placed in a water bath – and the mixture was not heated, but stirred at room temperature for one month. The yield was 33.8%. Example 7 Synthesis of diethylcarbamoyloxydiphenylphosphine 13

[0120] Diethylcarbamoyloxydiphenylphosphine 13 was prepared according to the procedure shown in Scheme B-7. Diethylcarbamoyloxytrimethylsilane 4 was prepared as described in Example 2.

[0121] Under ice-cooled and stirring conditions, 5.030 g (22.797 mmol) of diphenylchlorophosphine 12 were added dropwise to 6.421 g (33.914 mmol) of diethylcarbamoyloxytrimethylsilane 4. The mixture was stirred at room temperature for one week. The yield of compound 13 was 8.4% according to NMR (based on the chlorophosphine 12).

[0122] NMR data for compound 13 31 P-NMR: (162 MHz, CDCl3) δ = 99.8 (P 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) δ = 154.5 (d, C 1 , J C1-P = 9.1 Hz), 140.2 (d, C 2 , J C2-P = 19.8 Hz), 130.9 (d, C 3 , J C3-P = 23.7 Hz), 129.7 (C 4 ), 128.4 (d, C 5 , J C5-P = 7.1 Hz), 42.2 (C 6 ), 42.0 (C 7 ), 14.2 (C 8 ), 13.9 (C 9 ), ppm. Examples 8 and 9

[0123] Examples 8 and 9 illustrate the oxidations of carbamoyloxyphosphanes to compounds of general formula I. Example 8 Synthesis of Bis(diethylamino)diethylcarbamoyloxyphosphane oxide 14

[0124] Bis(diethylamino)diethylcarbamoyloxyphosphine oxide 14 is a compound of general formula I and was prepared by oxidation of bis(diethylamino)diethylcarbamoyloxyphosphine 9 with hydrogen peroxide according to the procedure shown in Scheme B-8. Bis(diethylamino)diethylcarbamoyloxyphosphine 9 was prepared as described in Example 5.

[0125] To a solution of 1.080 g (3.707 mmol) of bis(diethylamino)diethylcarbamoyloxyphosphane 9 in 10 ml of tetrahydrofuran (THF), 0.390 g (3.439 mmol) of 30% hydrogen peroxide solution in 10 ml of THF were slowly added dropwise while the mixture was cooled on ice and stirred. The mixture was then warmed to room temperature and stirred for 2 h. Finally, all volatile components were removed under vacuum, and 0.880 g of bis(diethylamino)diethylcarbamoyloxyphosphane oxide 14 was obtained as a colorless liquid (77.2% yield).

[0126] NMR- und IR-Daten für Verbindung 14 31 P-NMR: (162 MHz, CDCl3) δ = 12,3 (P 1 ) ppm. 13 C-NMR: (126 MHz, CDCl3) δ = 149,8 (d, C 1 , J C1-P = 3,2 Hz), 42,3 (C 2 ), 42,1 (C 3 ), 39,8 (d, C 4 , J C4-P = 4,8 Hz), 14,3 (C 5 ), 14,2 (C 6 ), 14,0 (d, C 7 , J C7-P = 2,7 Hz) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 3,00 (m, 4H, H(C 2 +C 3 )), 2,81 (m, 8H, H(C 4 ), 0,89 (m, 6H, H(C 5 +C 6 )), 0,83 (m, 12H, H(C 7 )) ppm. IR: (ATR) v = 657,6 (w, v sym PNC

[20] ), 709,7 (m), 783,0 (s, v sym POC

[20] ), 825,4 (m), 935,4 (vs), 956,6 (vs), 1024,1 (vs, v as PNC

[20] ), 1122,4 (s, v as POC

[20] ), 1149,4 (s, v C-O in COP

[20] ), 1211,1 (m), 1245,9 (s, v P=O

[20] ), 1378,9 (m), 1417,5 (m), 1710,6 (vs, v C=O), 2970,0 (w, v NCH

[20] ) cm-1 . Example 9 Synthesis of Bis(diethylamino)diethylcarbamoyloxyphosphane oxide 14

[0127] In this example, bis(diethylamino)diethylcarbamoyloxyphosphine oxide 14 was prepared by using oxygen instead of hydrogen peroxide for the oxidation of bis(diethylamino)diethylcarbamoyloxyphosphine 9 (Scheme B-9). Bis(diethylamino)diethylcarbamoyloxyphosphine 9 was prepared as described in Example 5.

[0128] Under protective gas, 1.100 g (3.775 mmol) of bis(diethylamino)diethylcarbamoyloxyphosphane 9 were dissolved in approximately 40 ml of hexane and subjected to oxygen pressure of 10 bar (1000 kPa) in an autoclave. The mixture was stirred for one week, after which the autoclave was depressurized. The solution was decanted from the separated red oil, and subsequently, all volatile components were removed by condensation in a cold trap. 1.000 g of bis(diethylamino)diethylcarbamoyloxyphosphane oxide 14 was obtained as a colorless liquid (86.2% yield).

[0129] NMR data for compound 14 31 P-NMR: (162 MHz, CDCl3) δ = 12.3 (P 1 ) ppm. 13 C-NMR: (126 MHz, CDCl3) δ = 149.8 (d, C1, J C1-P = 3.1 Hz), 42.2 (C 2 ), 42.1 (C 3 ), 39.8 (d, C 4 , J C4-P = 4.6 Hz), 14.3 (C 5 ), 14.2 (C 6 ), 13.8 (d, C 7 , J C7-P = 2.7 Hz) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 3.31 (m, 4H, H(C2 +C 3 )), 3.12 (m, 8H, H(C 4 ), 1.20 (t, 6H, H(C 5 +C 6 )), 1.14 (t, 12H, H(C 7 )) ppm. Examples 10 to 12

[0130] Examples 10 to 12 illustrate the preparation of compounds of general formula I from metal or semimetal carbamates. Example 10 Synthesis of N,N-Diethylcarbamoyloxydiphenoxyphosphine oxide PB-167

[0131] N,N-Diethylcarbamoyloxydiphenoxyphosphane oxide PB-167 was prepared from diethylcarbamoyloxytrimethylsilane 4 according to the procedure shown in Scheme B-10. Diethylcarbamoyloxytrimethylsilane 4 was obtained as described in Example 2.

[0132] 1.449 g (5.394 mmol) of diphenyl chlorophosphate 21 were slowly added dropwise to 1.000 g (5.282 mmol) of diethylcarbamoyloxytrimethylsilane 4. The mixture was then stirred for three months and an NMR sample was taken. 31P-NMR showed the conversion of chlorophosphate 15 51.3% to 34.6% N,N-diethylcarbamoyloxydiphen-oxyphosphane oxide PB-167.

[0133] NMR data for compound PB-167 31 P-NMR: (162 MHz, CDCl3) δ = -19.4 ppm. 13 C-NMR: (101 MHz, CDCl3) δ = 150.3 (d, C 1 , J C1-P (= 7.5 Hz) 147.3 (d, C 2 , J C2-P = 3.8 Hz), 129.9, 129.8, 129.7, 129.4, 126.3, 125.9, 125.6, 124.5, 120.3 (m), 120.0 (m), 42.6 (C 3 ), 42.5 (C 3 ), 13.6 (C 4 ), 12.7 (C 4 ) ppm. 1 H-NMR: (400 MHz, CDCl3) δ = 7.03-7.38 (m, H(Ar)), 2.82-3.44 (m, H(C 3 )), 0.88-1.18 (m, H(C 4 ) ppm. The assignment of some signals was not possible due to signal overlap. Example 11 Synthesis of N,N-Diethylcarbamoyloxydiphenylphosphine oxide 17

[0134] N,N-Diethylcarbamoyloxydiphenylphosphine oxide 17 was prepared from diethylcarbamoyloxytrimethylsilane 4 according to the procedure shown in Scheme B-11. Diethylcarbamoyloxytrimethylsilane 4 was obtained as described in Example 2.

[0135] To 0.982 g (5.187 mmol) of diethylcarbamoyloxytrimethylsilane 4, 1.180 g (4.986 mmol) of chlorodiphenylphosphine oxide 16 were slowly added dropwise under stirring and protective gas. After three months, an NMR sample was taken. The chlorophosphine oxide (ClPOPh2) was converted to 84.5%, yielding 34.2% N,N-diethylcarbamoyloxydiphenylphosphine oxide 17.

[0136] NMR data for compound 17 31 P-NMR: (162 MHz, CDCl3) δ = 28.4 (P(Et2NCOOPOPh2)). 13 C-NMR: (101 MHz, CDCl3) δ = 149.0 (d, C 1 , Et2NCOOPOPh2, J C1-P= 5.2 Hz), 134.6, 133.4, 133.2, 132.9, 132.9, 132.4, 132.1, 132.1, 132.0, 131.9, 131.5, 131.4, 131.4, 131.3, 131.2, 131.1, 131.0, 130.7, 130.6, 130.1, 128.6, 128.5, 128.3, 128.2, 128.1, 128.1, 128.0, 45.4, 44.1, 42.3, 42.0, 41.5, 41.0, 13.9, 13.8, 13.7, 13.4, 13.1, 12.7, 12.5, 11.0, 2.9 ppm. 1 ¹H NMR: (400 MHz, CDCl3) δ = 7.03–7.63 ppm (m, H(Ar)), 2.65–3.20 ppm (m, H(N-CH2-)), 0.75–0.98 ppm (m, H(CH3 in NEt2)). Assigning some signals is not possible due to signal overlap. Example 12 Synthesis of N-methyl-N-phenylcarbamoyloxydiphenoxyphosphine oxide 19

[0137] N-Methyl-N-phenylcarbamoyloxydiphenoxyphosphine oxide 19 was prepared from lithium-N-methyl-N-phenylcarbamate 6 according to the procedure shown in Scheme B-12. Lithium-N-methyl-N-phenylcarbamate 6 was obtained as described in Example 3.

[0138] In 100 ml of THF, 6.7620 g (40.0 mmol) of lithium N-methyl N-phenylcarbamate 6 were suspended under protective gas, and at -20 °C, 10.512 g (39.1 mmol) of diphenyl chlorophosphate 18 in 50 ml of THF were added dropwise. The mixture was then filtered to remove the lithium chloride, and the THF was separated under vacuum by condensation in a cold trap. The residue was reconstituted in ethyl acetate and washed twice with water and once with saturated sodium bicarbonate solution. The crude product was recrystallized in ethyl acetate / petroleum ether, filtering off the insoluble black residue (oxidation product of lithium amide). Product 19 was obtained as large, colorless prisms (11.48 g; 76.6% yield based on the chlorophosphate 18), which could also be used for single-crystal X-ray diffractometry. m = 55 °C.

[0139] NMR and IR data for compound 19 31 P-NMR: (162 MHz, CDCl3) δ = -20.14 (P 1 ) ppm. 13C-NMR: (101 MHz, CDCl3) δ = 150,4 (d, C 1 , J C1-P = 7,9 Hz), 147,4 (C 2 ), 141,8 (C 3 ), 129,8 (C 4 ), 129,6 (C 5 ), 127,9 (C 6 ), 126,6 (C 7 ), 125,8 (C 8 ), 120,5 (d, C 9 , J C9-P = 4,7 Hz), 38,8 (C 10 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 7,40-6,93 (m, 15H, H(Ar)), 3,24 (s, 3H, H(C 10 )) ppm. IR: (ATR) v = 615,2 (w), 661,5 (m, δ POAr

[20] ), 684,6 (s, δ CNC

[20] ), 705,9 (m), 748,3 (vs, vs POAr

[20] ), 871,7 (m), 900,6 (m), 939,2 (vs, v s POC

[20] ), 960,4 (vs, v as POAr), 993,2 (w), 1008,6 (w), 1026,0 (w), 1083,9 (m), 1122,4 (w, v POC

[20] ), 1170,6 (m, v P=O

[20] ), 1216,9 (w, v C-O in COP

[20] ), 1284,4 (w), 1299,9 (w), 1378,9 (w), 1417,5 (vw), 1456,1 (w), 1486,9 (m), 1593,0 (w), 1751,1 (m, v C=O) cm -1 . Beispiele 13 bis 19

[0140] Examples 13 to 19 illustrate the synthesis of phosphoryl carbamates from a phosphoryl chloride, a secondary amine, and carbon dioxide in the presence of an auxiliary base. The following general synthesis procedure was followed. General synthesis procedure for the preparation of phosphorylcarbamates

[0141] 1 to 1.2 molar fractions of the dialkylamine (for work-up B) are dissolved with 2 molar fractions of triethylamine in five times its volume of dry THF. The solution is then subjected to CO₂ at 8 bar (800 kPa) with stirring for at least 1.5 h. Alternatively, CO₂ can be introduced at atmospheric pressure until saturation is reached. Depending on the amine and batch size, this can take up to a full day due to the slow carbamate formation. The ammonium carbamate formed in this way is not isolated. Its solution is diluted to three times its volume with dry THF and cooled to -78 °C (for example, using a dry ice-isopropanol cooling mixture). Then, one molar fraction of the phosphoryl chloride is slowly added dropwise over three hours in five times its volume of dry THF. After the addition is complete, the mixture is stirred for another hour at -78 °C.Alternatively, cooling can be carried out with dry ice / acetonitrile at -40 °C or even higher temperatures, however, this results in an increased formation of aminophosphine oxide as a byproduct, which is sometimes difficult to separate from the target compound and can be carcinogenic (except when using phosphoryl chlorides with high oxidation states on the phosphorus and sterically demanding amines).

[0142] The work-up process distinguishes between A) hydrolysis-sensitive phosphorylcarbamates (these are mainly compounds with low oxidation states) and B) hydrolysis-insensitive phosphorylcarbamates.

[0143] Work-up A) The precipitated hydrochloride is filtered off, and the solvent is separated by condensation in a cold trap under vacuum. If the target compound still contains hydrochloride, the remaining residue is extracted with a nonpolar solvent (e.g., benzene, diethyl ether, or dichloromethane), filtered to remove any remaining ammonium salts, and the solvent is rapidly removed under vacuum. The crude product can be recrystallized if necessary. This work-up procedure is applicable to all target compounds.

[0144] Work-up B) The reaction mixture is treated with half the volume of ethyl acetate to precipitate further ammonium salts. These are filtered off, and the reaction mixture is washed with 5% HCl, water, saturated sodium bicarbonate solution, and water, and dried over sodium sulfate. The solvent is removed by rotary evaporator, and a clean product is obtained. Example 13 Synthesis of N,N-Dibenzylcarbamoyloxydiphenoxyphosphine oxide PB-163

[0145] The synthesis of N,N-Dibenzylcarbamoyloxydiphenoxyphosphine oxide PB-163 is illustrated in Scheme B-13.

[0146] 3.034 g (15.4 mmol) of dibenzylamine 20 were dissolved together with 3.131 g (30.9 mmol) of triethylamine in approximately 40 ml of THF and subjected to 8 bar (800 kPa) of CO2 pressure in an autoclave. After two hours, the autoclave was depressurized. The solution was transferred and 50 ml of THF were added. The mixture was then cooled to -78 °C, and 4.067 g (15.1 mmol) of diphenylchlorophosphate 18 in 40 ml of THF were slowly added dropwise over two hours. The mixture was stirred for another hour at this temperature and then warmed to room temperature. Approximately 75 ml of ethyl acetate were then added and filtered off the hydrochloride. The mixture was then washed with 5% HCl, water, saturated sodium bicarbonate solution, and water, and dried over sodium sulfate. After removal of the solvent using a rotary evaporator, 5.631 g (81.0% yield, based on the chlorophosphate) of product PB-163 were obtained as a colorless solid. m= 71 °C. The product could be recrystallized in chloroform / pentane to obtain single crystals for X-ray diffractometry.

[0147] NMR and IR data for compound PB-163 31 P-NMR: (162 MHz, CDCl3) δ= -19.61 (P 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) δ= 150.32 (d, C 1 , J C1-P = 7.4 Hz), 148.67 (d, C 2 , J C2-P = 3.7 Hz), 135.60 (C 3 ), 135.44 (C 3 ), 129.9 (C 4 ), 128.9 (C 5 ), 128.8 (C 5 ), 128.4 (C 6 ), 128.1 (C 7 ), 127.9 (C 7 ), 127.3 (C 6 ), 125.7 (C 8 ), 120.33 (d, C 9 , J C9-P = 4.8 Hz), 50.0 (C 10 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 7.02-7.36 (m, 10H, H(Ar)), 4.44 (s, 2H, H(C 10 )), 4.27 (s, 2H, H(C 10 )), ppm. IR: (ATR) v = 615.2 (m, δPOAr

[20] ), 686.6 (vs, δCNC

[20] ), 750.2 (s, v s POAr

[20] ), 769.5 (s, out of plane δ 5 Ar-H

[20] ), 821.6 (w, out of plane δ 5 Ar-H

[21] ), 840.9 (f), 877.5 (vs), 912.2 (m), 941.1 (vs, v s COP

[20] ), 966.2 (vs, v as POAr

[20] ), 985.5 (vw), 1010.6 (m), 1056.9 (m), 1083.9 (m), 1157.1 (m, v POAr

[20] ), 1180.3 (s, v P=O), 1207.3 (m, v OAr in POC

[20] ), 1234.3 (w, v CO in COP

[20] ). (vw) cm -1 . Example 14 Synthesis of N,N-Diethylcarbamoyloxydiphenoxyphosphine oxide PB-167

[0148] As an alternative to Example 10, the synthesis of N,N-diethylcarbamoyloxy-diphenoxyphosphine oxide PB-167 was carried out according to Scheme B-14.

[0149] 5.968 g (31.6 mmol) of diethylamine 21 were dissolved together with 17.300 g (171.0 mmol) of triethylamine in approximately 40 ml of THF and subjected to 8 bar (800 kPa) of CO2 pressure in an autoclave. After two hours, the autoclave was depressurized. The solution was transferred and 50 ml of THF were added. The mixture was then cooled to -78 °C, and over two hours, 15.500 g (57.7 mmol) of diphenyl chlorophosphate 18 in 40 ml of THF were slowly added dropwise. The mixture was stirred for another hour at this temperature and then warmed to room temperature. Approximately 75 ml of ethyl acetate were then added and filtered off the hydrochloride. The mixture was then washed with 5% HCl, water, saturated sodium bicarbonate solution, and water, and dried over sodium sulfate. After removal of the solvent using a rotary evaporator, 15.060 g (74.7% yield, based on the chlorophosphate) of product PB-167 was obtained as a colorless liquid.

[0150] NMR and IR data for compound PB-16731 P-NMR: (162 MHz, CDCl3) δ= -19,39 (P 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) (5= 150,46 (d, C 1 , J C1-P = 7,4 Hz), 147,5 (d, C 2 , J C2-P = 3,8 Hz), 129,8 (C 3 ), 125,7 (C 4 ), 120,4 (d, C 5 , J C5-P = 5,8 Hz), 42,7 (C 6 ), 42,7 (C 6 ), 13,8 (C 7 ), 12,9 (C 7 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ= 7,38-7,17 (m, 10H, H(Ar)), 3,30 (q, 2H, H(C 6 )), 3,15 (m, 2H, H(C 6 )), 1,15 (t, 3H, H(C 7 )), 1,01 (t, 3H, H(C 7 )) ppm. IR: (ATR) v = 632,6 (w, δPOAr

[20] ), 690,4 (w, δCNC

[20] ), 767,6 (vw, v s POAr

[20] ), 860,1 (vw), 935,4 (vs, v as POAr

[20] ), 962,4 (vs, v as POC

[20] ), 1010,6 (w), 1026,0 (w), 1039,5 (w), 1141,7 (m, v POAr), 1161,0 (m, v C-O in COP

[20] ), 1186,1 (s, P=O

[20] ), 1216.9 (w), 1269.0 (w), 1303.7 (m), 1382.8 (vw), 1421.4 (w), 1456.1 (w), 1486.9 (s), 1589.1 (w), 1735.7 (vs, v C=O), 2975.7 (w) cm -1 . Example 15 Synthesis of N,N-Dibenzylcarbamoyloxydiphenylphosphine oxide PB-165

[0151] The synthesis of N,N-dibenzylcarbamoyloxydiphenylphosphine oxide PB-165 was carried out according to Scheme B-15.

[0152] 5.984 g (30.3 mmol) of dibenzylamine 20 were dissolved together with 6.187 g (61.1 mmol) of triethylamine in approximately 40 ml of THF and subjected to 8 bar (800 kPa) of CO2 pressure in an autoclave. After two hours, the autoclave was depressurized. The solution was transferred and 50 ml of THF were added. The mixture was then cooled to -78 °C, and 7.177 g (30.3 mmol) of diphenylchlorophosphine oxide 22 in 40 ml of THF were slowly added dropwise over two hours. The mixture was stirred at this temperature for another hour and then warmed to room temperature. The hydrochloride was then filtered off, and the solvent was separated by condensation in a cold trap under vacuum. The crude product was stirred in 200 ml of benzene for 6 hours and filtered off the insoluble residue. The solvent was removed using a rotary evaporator, and 12.990 g of product PB-165 (86.3% yield, based on the phosphoryl chloride 22) were obtained as a colorless solid. m= 99 °C. The product PB-165 was obtained in sufficiently pure form, but could be recrystallized in dry diethyl ether if necessary (not suitable for recrystallization are: isopropanol and other alcohols, acetonitrile, acetonitrile / pentane, ethyl acetate, ethyl acetate / petroleum ether, benzene, benzene / petroleum ether, acetone, THF, chloroform and dichloromethane).

[0153] Although the product is storable in air, it was slowly hydrolyzed by water, and was particularly sensitive in solution. At the same time, the hydrolysis product, dibenzylammonium diphenylphosphinate, was not water-soluble, which is why this compound cannot be purified via workup A.

[0154] NMR and IR data for compound PB-165 31 P-NMR: (162 MHz, CDCl3) δ = 29.3 (P 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) δ = 150.52 (d, C 1 , J C1-P = 5.3 Hz), 136.4 (C 2 ), 136.0 (C 2 ), 132.5 (d, C 2 , J C3-P= 2,9 Hz), 131,4 (d, C 4 , J C4-P = 10,9 Hz), 131,1 (C 5 ), 130,0 (C 5 ), 128,9 (C 6 ), 128,6 (d, C 1 , J C7-P = 12,7 Hz), 128,5 (C 8 ), 128,4 (C 8 ), 127,9 (C 9 ), 127,8 (C 9 ), 127,0 (C 6 ), 50,3 (C 10 ), 50,1 (C 10 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ = 7,70-7,76 (m, 4H, H(C 4 )), 7,16-7,53 (m, 16H, H(C 5 -C 9 )), 4,47 (s, 2H, H(C 10 )), 4,45 (s, 2H, H(C 10 )) ppm. IR: (ATR) v = 690,4 (vs, δ CNC

[20] ), 725,1 (s, δout of plane CH in P-Ar

[20] ), 740,6 (m), 860,1 (s, v s

[20] ) COP, 937,3 (w), 960,4 (w), 1049,1 (m, v as POC

[20] ), 1081,9 (m), 1126,3 (m, v C-O in COP

[20] ), 1218,9 (s, v P=O

[20] ), 1240,1 (m), 1415,6 (m), 1438,7 (w), 1494,6 (w), 1710,7 (s, C=O) cm -1 . Example 16 Synthesis of N,N-Diethylcarbamoyloxydiphenylphosphine oxide 17

[0155] As an alternative to Example 11, the synthesis of N,N-diethylcarbamoyloxydiphenylphosphine oxide 17 was carried out according to Scheme B-16.

[0156] 4.303 g (58.8 mmol) of diethylamine 21 were dissolved together with 10.001 g (98.8 mmol) of triethylamine in approximately 40 ml of THF and subjected to 8 bar (800 kPa) CO2 pressure in an autoclave. After two hours, the autoclave was depressurized. The solution was transferred and 50 ml of THF were added. The mixture was then cooled to -78 °C, and 11.603 g (49.0 mmol) of diphenylchlorophosphine oxide 22 in 40 ml of THF was slowly added dropwise over two hours. The mixture was stirred at this temperature for another hour and then warmed to room temperature. The hydrochloride was then filtered off, and the solvent was separated by condensation in a cold trap under vacuum. The crude product was stirred in 200 ml of benzene for 6 hours and filtered off the insoluble residue. The solvent was removed using a rotary evaporator, and 9.413 g of product 17 (70.4% yield, based on phosphoryl chloride 22) were obtained as a colorless solid. m= 77 °C. Although the product can be stored in air, it has been slowly hydrolyzed by water, which is why processing method A) is unsuitable.

[0157] NMR and IR data for compound 17 31 P-NMR: (162 MHz, CDCl3) δ= 28.4 (P 1 ) ppm. 13 C-NMR: (101 MHz, CDCl3) δ= 149.2 (d, C 1 , J C1-P = 5.3 Hz), 132.4 (C 2 ), 131.7 (C 3 ), 131.3 (d, C 4 , J C4-P = 10.6 Hz), 130.3 (C 3 ), 128.6 (C 5 ), 42.6 (C 6 ), 42.3 (C 6 ), 14.2 (C 7 ), 13.0 (C 7 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ= 7.83 (m, 4H, H(C 4 )), 7.44 (m, 6H, H(C 5 +C 3 )), 3.37 (m, 2H, H(C 6 )), 3.26 (m, 2H, H(C 6 )), 1.20 (m, 3H, H(C 7 )), 1.08 (m, 3H, H(C 7 )) ppm. IR: (ATR) v = 630.6 (m, δ CNC

[20] ), 696.2 (m), 725.1 (m, δ out of plane CH in P-Ar

[20] ), 754.1 (f), 835.1 (m), 954.6 (s), 1039.5 (m, v as POC

[20] ), 1108.9 (m), 1128.2 (s, v CO in COP), 1145.6 (m), 1236.2 (s, v P=O

[20] ), 1269.0 (m), 1419.4 (m), 1438.7 (m), 1718.4 (vs, v C=O) cm -1 . Example 17 Synthesis of 10-(N,N-Dibenzylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantren-10-oxide PB-179

[0158] The synthesis of 10-(N,N-Dibenzylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantren-10-oxide PB-179 was carried out according to Scheme B-17.

[0159] 6.465 g (32.77 mmol) of dibenzylamine 20 were dissolved together with 6.744 g (66.6 mmol) of triethylamine in approximately 40 ml of THF and subjected to 8 bar (800 kPa) of CO2 pressure in an autoclave. After two hours, the autoclave was depressurized. The solution was transferred and 50 ml of THF were added. The mixture was then cooled to -78 °C, and over two hours, 8.251 g (32.9 mmol) of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide 2 (DOPO-Cl) in 40 ml of THF were slowly added dropwise. The mixture was stirred for another hour at this temperature and then warmed to room temperature. Approximately 75 ml of ethyl acetate were then added and filtered off the hydrochloride. The product was then washed with 5% HCl, water, saturated sodium bicarbonate solution and water, and dried over sodium sulfate.After removal of the solvent using a rotary evaporator, recrystallization was carried out in ethyl acetate, and 10.740 g (71.7% yield, based on the phosphoryl chloride 2) of product PB-179 were obtained as colorless crystals. m = 126 °C.

[0160] NMR and IR data for compound PB-179 31 P-NMR: (162 MHz, CDCl3) δ = 5.6 (P 1 ) ppm. 13 C-NMR: (101 MHz,CDCl3) δ= 149.9 (d, C 1 , J C1-P = 8.6 Hz), 149.7 (d, C 2 , J C2-P = 3.0 Hz), 137.1 (d, C 2 , J C3-P = 7.7 Hz), 135.7 (C 4 ), 135.6 (C 4 ), 134.2 (C 5 ), 132.7 (d, C 1 , J C6-P = 10.0 Hz), 130.8 (C 7 ), 128.8 (C 8 ), 128.8 (C 8 ), 128.5 (d*, C 9 ), 128.4 (C 10 ), 128.0 (C 11 ), 127.8 (C 11 ) 127.8 (C 10 ), 125.4 (C 12 ), 125.3 (C 13 ) 124.0 (d, C 14 , JC14-P = 12.5 Hz), 122.7 (d, C 15 , J C15-P = 12.2 Hz), 121.6 (d, C 16 , J C16-P = 178.8 Hz), 120.3 (d, C 17 , J C17-P = 7.1 Hz), 49.9 (C 18 ), 49.5 (C 18 ) ppm. 1 H-NMR: (500 MHz, CDCl3) δ= 8.16 (dddd, 1H, H(C 14 )), 7.90 (t, 1H, H(C 12 )), 7.86 (d, 1H, H(C 6 )), 7.69 (t, 1H, H(C 4 )), 7.50 (td, 1H, H(C 9 )) 7.02-7.33 (m, 11H, H(C 7 -C 8 -C 10 +C 13 +C 17 )) 6.73 (m, 2H, C 11 ), 3.90-4.40 (m, 4H, H(C 18 )) ppm. No coupling constants could be determined, since the signal from C 10 -Signal was superimposed. IR: (ATR) v = 617.1 (m, δ POAr

[20] ), 655.7 (m), 700.1 (vs, δ CNC

[20] ), 715.5 (m), 748.3 (vs, v as POAr

[20] ), 759.9 (s, δ out of plane CH in P-Ar

[20] ), 790.7 (s, v Cp

[20] ), 838.9 (vs., v. s POC

[20] ), 937.3 (s, v POC

[20] ), 1033.7 (s, v as POC

[20] ), 1083.9 (m), 1116.6 (w), 1155.2 (w), 1189.9 (s, v P=O

[20] ), 1211.1 (m), 1278.6 (m), 1294.1 (s, v CO in COP

[20] ), 1415.6 (m), 1448.4 (m), 1475.4 (w), 1598.8 (w), 1714.5 (vs, v C=O) cm -1 . Example 18 Synthesis of 10-(N,N-Diethylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide PB-175

[0161] The synthesis of 10-(N,N-Diethylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantren-10-oxide PB-175 was carried out according to Scheme B-18.

[0162] 4.055 g (55.4 mmol) of diethylamine 21 were dissolved together with 9.909 g (97.9 mmol) of triethylamine in approximately 40 ml of THF and subjected to 8 bar (800 kPa) of CO2 in an autoclave. After two hours, the autoclave was depressurized. The solution was transferred and 50 ml of THF were added. The mixture was then cooled to -78 °C, and over two hours, 11.347 g (45.3 mmol) of 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide 2 (DOPO-Cl) in 40 ml of THF were slowly added dropwise. The mixture was stirred for another hour at this temperature and then warmed to room temperature. Approximately 75 ml of ethyl acetate were then added and filtered off the hydrochloride. The mixture was then washed with 5% HCl, water, saturated sodium bicarbonate solution, and water, and dried over sodium sulfate. After removal of the solvent using a rotary evaporator, 10.340 g (68.9% yield, based on phosphoryl chloride 2) of product PB-175 were obtained as colorless crystals. m= 100 °C.

[0163] NMR and IR data for compound PB-175 31 P-NMR: (162 MHz, DMSO-d6) δ= 4.5 (P 1 ) ppm. 13 C-NMR: (101 MHz, DMSO-d6) δ = 149.2 (d, C 1 , J C1-P = 8.8 Hz), 147.6 (d, C 2 , J C2-P = 3.3 Hz), 136.3 (d, C 3 , J C3-P = 7.5 Hz), 134.5 (d, C 4 , J C4-P = 2.5 Hz), 131.6 (d, C 5 , J C5-P = 10.0 Hz), 131.1 (C 6 ), 128.6 (d, C 7 , J C7-P = 15.7 Hz), 126.0 (C 8 ), 125.5 (C 9 ), 124.7 (d, C 10 , J C10-P = 12.0 Hz), 122.2 (d, C 11 , J C11-P = 4.7 Hz), 121.2 (d, C 12 , J C12-P = 171.7 Hz), 119.7 (d, C 13 , J C13-P = 6.7 Hz), 42.1 (C 14 ), 41.8 (C 14 ), 13.2 (C 15 ), 12.7 (C 15 ) ppm. 1 H-NMR: (500 MHz, DMSO-d6) δ= 8.21 (m, 2H, H(C 10 +C 8 )), 8.00 (m, 1H, H(C 5)), 7,87 (m, 1H, H(C 4 )), 7,65 (m, 1H, H(C 7 )) 7,51 (m, 1H, H(C 6 )) 7,38 (m, 2H, H(C 9 +C 13 )), 2,82-3,17 (m, 4H, H(C 14 )), 0,92 (t, 3H, H(C 15 )), 0,68 (t, 3H, H(C 15 )) ppm. IR: (ATR) v = 621,0 (w, δPOAr

[20] ), 717,4 (s, δ CNC

[20] ), 750,2 (vs, v as POAr

[20] ), 796,5 (vs, v C-P

[21] ), 838,9 (vs, v as POC

[20] ), 923,8 (vs, v s P OC

[20] ), 946,9 (m), 964,3 (m), 1041,4 (m, v as POC

[20] ), 1080,0 (w), 1118,6 (m), 1149,4 (s, v P=O

[20] ), 1197,6 (m), 1267,1 (s, v C-O in COP

[20] ), 1294,1 (s), 1419,4 (m), 1477,3 (m), 1712,6 (vs, v C=O) cm -1 . Beispiel 19Untersuchung der Flammschutzeigenschaften

[0164] The flame-retardant properties of the compounds N,N-dibenzylcarbamoyloxydiphenoxyphosphane oxide (PB-163), N,N-diethylcarbamoyloxydiphenoxyphosphane oxide (PB-167), 10-(N,N-diethylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (PB-175), and 10-(N,N-dibenzylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (PB-179) were investigated. For this purpose, each compound was incorporated into a polymer to obtain compounds. The polymer was either polystyrene (PS) or polylactic acid (PLA). The compounds consisting of the polymer and one of the aforementioned compounds were then injection-molded into test specimens. Compound PB-165 was also incorporated into polylactide and processed into test specimens using injection molding. The results are shown in Tables FS-1 and FS-2.

[0165] The polystyrene used was powdered polystyrene, commercially available under the trade name Styrolution PS 158K from INEOS Styrolution, Frankfurt am Main, Germany. The polystyrene was mixed manually with the flame retardant and then compounded at 170 °C using a mini-extruder, commercially available under the name MiniLab from Thermo-Haake, Karlsruhe, Germany, at a speed of 50 revolutions per minute (rpm). Test specimens were then produced from the resulting compound at 175 °C using an injection molding machine, commercially available under the name MiniJet II from Thermo Scientific, Karlsruhe, Germany.

[0166] The polylactide used was powdered polylactide, commercially available under the trade name Luminy LX975 from TotalEnergies Corbion, NS Gorinchem, NL. The polylactide was manually mixed with the flame retardant and then compounded using a mini-extruder, commercially available under the name MiniLab from Thermo-Haake, Karlsruhe, DE, at a speed of 100 rpm and 160 °C. Test specimens were then produced from the resulting compound at 155 °C using an injection molding machine, commercially available under the name MiniJet II from Thermo Scientific, Karlsruhe, DE.

[0167] The test specimens were evaluated using the limiting oxygen index (LOI) test. The LOI test was performed as described in DIN EN ISO 4589-2:2017-11 (Determination of combustion behavior by the oxygen index: Limiting Oxygen Index, LOI). The exemplary compounds demonstrated a flame-retardant effect. This was evident from the increased LOI value of the flame-retardant-containing material compared to the flame-retardant-free material.

[0168] In tables FS-1 and FS-2, the value “LOI / O2 (%)” indicates the minimum oxygen concentration in volume percent at which 50% of the test specimens burn. Details, particularly regarding test conditions, specimen size, pretreatment, and the definition of “burning,” can be found in DIN EN ISO 4589-2:2017-11. The value “Flame retardant (wt%)” indicates the percentage by weight of the flame retardant in relation to the total weight of the respective compound. Table FS-1: Flame retardancy results in polystyrene LOI / O2(%) Flame retardant (wt%) PS (without flame retardant) 21,1 ± 0,38 - PS PB-163 23,9 ± 0,38 10 PS PB-167 24,1 ± 0,38 10 PS PB-175 22,9 ± 0,38 10 PS PB-179 22,9 ± 0,38 10 Table FS-2: Flame retardancy results in polylactide LOI / O2(%) Flame retardant (wt%) PLA (without flame retardant) 24,1 ± 0,38 - PLA myth PB-163 25,1 ± 0,38 10 PLA myth PB-167 25,4 ± 0,38 10 PLA myth PB-175 27,5 ± 0,40 10 PLA myth PB-179 27,5 ± 0,40 10 PLA myth PB-165 28,8 ± 0,27 10 Example 20: Investigation of bearing stability

[0169] The storage stability of the compounds N,N-dibenzylcarbamoyloxydiphenoxyphosphine oxide (PB-163), N,N-diethylcarbamoyloxydiphenoxyphosphine oxide (PB-167), 10-(N,N-diethylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (PB-175), and 10-(N,N-dibenzylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (PB-179) was investigated. For this purpose, the compounds were each left at room temperature in ambient air for three months. Subsequently, the compounds were analyzed by NMR. No changes were observed. literature [1] Z. WANG, WE ZHANG, CN117736539A, 2024. [2] CM Allen, J. Jamieson, “The hydrolysis of N-aryl carbamyl phosphate monoand dianions,” J. Am. Chem. Soc. 1971, 93, 1434-1441, DOI 10.1021 / ja00735a019. [3] CM Allen, ME Jones, “Decomposition of carbamylphosphate in aqueous solutions,” Biochem. 1964, 3, 1238-1247, DOI 10.1021 / bi00897a010. [4] R. W. Balsiger, D. G. Jones, J. A. Montgomery, „Synthesis ofpotential anticancer agents. XVIII. Analogs of carbamoyl phosphate“, J. Org. Chem. 1959, 434. [5] F. Cramer, M. Winter, „Zur Chemie der „energiereichen Phosphate“, VIII. Carbamylphosphate", Chem. Ber. 1959, 92, 2761-2767, DOI 10.1002 / cber.19590921114. [6] A. Lapidot, D. Samuel, „372. Kinetic and isotopic studies of the hydrolysis of NN-diethylcarbamoyl phosphate“, J. Chem. Soc. 1964, 1931, DOI 10.1039 / jr9640001931. [7] F. Seel, N. Klein, „N-Methylcarbamoylphosphate, I. Synthese / N-Methylcarbamoyl Phosphates, I. Synthesis“, Z. Naturforsch. B 1983, 38, 797-803, DOI 10.1515 / znb-1983-0701. [8] F. Seel, N. Klein, „N-Methylcarbamoylphosphate, II. Thermische Zersetzung / N-Methylcarbamoyl Phosphates, II. Thermal Decomposition“, Z. Naturforsch. B 1984, 39, 1095-1099, DOI 10.1515 / znb-1984-0819. [9] Farbenfabriken Bayer A.-G., GB991979, 1965.

[10] G. Oertel, H. Holtschmidt, CH422777A, 1966.

[11] G. Oertel, H. Malz, H. Holtschmidt, DE1172260B, 1964.

[12] E. Garcia-Egido, M. Fernandez-Suarez, L. Munoz, „Synthesis of carbamoyl azides from primary amines and carbon dioxide under mild conditions“, J. Org. Chem. 2008, 73, 2909-2911, DOI 10.1021 / jo702506v.

[13] E. Garcia-Egido, J. Paz, B. Iglesias, L. Munoz, „Synthesis of cyanoformamides from primary amines and carbon dioxide under mild conditions. Synthesis of ceratinamine“, Org. Biomol. Chem. 2009, 7, 3991-3999, DOI 10.1039 / b912043b.

[14] J. Paz, C. Perez-Balado, B. Iglesias, L. Munoz, „Carbonylation with CO2 and Phosphorus Electrophiles: A Convenient Method for the Synthesis of 2-Oxazolidinones from 1,2-Amino Alcohols“, Synlett 2009, 2009, 395-398, DOI 10.1055 / s-0028-1087531.

[15] J. Paz, C. Perez-Balado, B. Iglesias, L. Munoz, „Carbon dioxide as a carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas: scope and limitations“, J. Org. Chem. 2010, 75, 3037-3046, DOI 10.1021 / jo100268n.

[16] K. A. Salmeia, G. Baumgartner, M. Jovic, A. Gössi, W. Riedl, T. Zich, S. Gaan, „Industrial Upscaling of DOPO-Based Phosphonamidates and Phosphonates Derivatives Using C12 Gas as a Chlorinating Agent“, Organic Process Research & Development 2018, 22, 1570-1577, DOI 10.1021 / acs.oprd.8b00295.

[17] K. Kraushaar, C. Wiltzsch, J. Wagler, U. Böhme, A. Schwarzer, G. Roewer, E. Kroke, „From CO2 to Polysiloxanes: Di(carbamoyloxy)silanes Si((OCO)NRR)2 as Precursors for PDMS“, Organometallics 2012, 31, 4779-4785, DOI 10.1021 / om300313f.

[18] R. Okawara, DE Webster, EG Rochow, "The Infrared Spectra of the Methylacetoxysilanes and Some Methyltin Carboxylates. The Configuration of the Trimethyltin and the Dimethyltin Cations", J. Am. Chem. Soc. 1960, 82, 3287-3290, DOI 10.1021 / ja01498a013.

[19] G. Bresciani, L. Biancalana, G. Pampaloni, F. Marchetti, “Recent Advances in the Chemistry of Metal Carbamates”, molecules 2020, 25, DOI 10.3390 / molecules25163603.

[20] G. Socrates, Infrared and Raman characteristic group frequencies: Tables and charts, 3rd ed., Wiley, Chichester and Weinheim, 2001. QUOTES INCLUDED IN THE DESCRIPTION

[0000] This list of documents cited by the applicant was automatically generated and is included solely for the reader's convenience. The list is not part of the German patent or utility model application. The DPMA accepts no liability for any errors or omissions. Zitierte Patentliteratur

[0000] CN 117736539 A [0004, 0169] GB 991 979 A

[0006] CH 422 777A [0006, 0169] DE 11 72 260 B

[0006] DE 1172260

[0169] Zitierte Nicht-Patentliteratur

[0000] DIN EN ISO 4589-2:2017-11

[0167] C. M. Allen, J. Jamieson, „The hydrolysis of N-aryl carbamyl phosphate monoand dianions“, J. Am. Chem. Soc. 1971, 93, 1434-1441, DOI 10.1021 / ja00735a019

[0169] C. M. Allen, M. E. Jones, „Decomposition of carbamylphosphate in aqueous Solutions“, Biochem. 1964, 3, 1238-1247, DOI 10.1021 / bi00897a010

[0169] R. W. Balsiger, D. G. Jones, J. A. Montgomery, „Synthesis ofpotential anticancer agents. XVIII. Analogs of carbamoyl phosphate“, J. Org. Chem. 1959, 434

[0169] F. Cramer, M. Winter, „Zur Chemie der „energiereichen Phosphate“, VIII. Carbamylphosphate", Chem. Ber. 1959, 92, 2761-2767, DOI 10.1002 / cber.19590921114

[0169] A. Lapidot, D. Samuel, „372. Kinetic and isotopic studies of the hydrolysis of NN-diethylcarbamoyl phosphate“, J. Chem. Soc. 1964, 1931, DOI 10.1039 / jr9640001931

[0169] F. Seel, N. Klein, „N-Methylcarbamoylphosphate, I. Synthese / N-Methylcarbamoyl Phosphates, I. Synthesis“, Z. Naturforsch. B 1983, 38, 797-803, DOI 10.1515 / znb-1983-0701

[0169] F. Seel, N. Klein, „N-Methylcarbamoylphosphate, II. Thermische Zersetzung / N-Methylcarbamoyl Phosphates, II. Thermal Decomposition“, Z. Naturforsch. B 1984, 39, 1095-1099, DOI 10.1515 / znb-1984-0819

[0169] E. Garcia-Egido, M. Fernandez-Suarez, L. Munoz, „Synthesis of carbamoyl azides from primary amines and carbon dioxide under mild conditions“, J. Org. Chem. 2008, 73, 2909-2911, DOI 10.1021 / jo702506v

[0169] E. Garcia-Egido, J. Paz, B. Iglesias, L. Munoz, „Synthesis of cyanoformamides from primary amines and carbon dioxide under mild conditions. Synthesis of ceratinamine“, Org. Biomol. Chem. 2009, 7, 3991-3999, DOI 10.1039 / b912043b

[0169] J. Paz, C. Perez-Balado, B. Iglesias, L. Munoz, „Carbonylation with CO2 and Phosphorus Electrophiles: A Convenient Method for the Synthesis of 2-Oxazolidinones from 1,2-Amino Alcohols“, Synlett 2009, 2009, 395-398, DOI 10.1055 / s-0028-1087531

[0169] J. Paz, C. Perez-Balado, B. Iglesias, L. Munoz, „Carbon dioxide as a carbonylating agent in the synthesis of 2-oxazolidinones, 2-oxazinones, and cyclic ureas: scope and limitations“, J. Org. Chem. 2010, 75, 3037-3046, DOI 10.1021 / jo100268n

[0169] K. A. Salmeia, G. Baumgartner, M. Jovic, A. Gössi, W. Riedl, T. Zich, S. Gaan, „Industrial Upscaling of DOPO-Based Phosphonamidates and Phosphonates Derivatives Using C12 Gas as a Chlorinating Agent“, Organic Process Research & Development 2018, 22, 1570-1577, DOI 10.1021 / acs.oprd.8b00295

[0169] K. Kraushaar, C. Wiltzsch, J. Wagler, U. Böhme, A. Schwarzer, G. Roewer, E. Kroke, „From CO2 to Polysiloxanes: Di(carbamoyloxy)silanes Si((OCO)NRR)2 as Precursors for PDMS“, Organometallics 2012, 31, 4779-4785, DOI 10.1021 / om300313f

[0169] R. Okawara, D. E. Webster, E. G. Rochow, „The Infrared Spectra of the Methylacetoxysilanes and Some Methyltin Carboxylates. The Configuration of the Trimethyltin and the Dimethyltin Cations“, J. Am. Chem. Soc. 1960, 82, 3287-3290, DOI 10.1021 / ja01498a013

[0169] G. Bresciani, L. Biancalana, G. Pampaloni, F. Marchetti, „Recent Advances in the Chemistry of Metal Carbamates“, molecules 2020, 25, DOI 10.3390 / molecules25163603

[0169] G. Socrates, Infrared and Raman characteristic group frequencies: Tables and charts, 3. Aufl., Wiley, Chichester und Weinheim, 2001

[0169]

Claims

[1] Use of a compound of general formula I as a flame retardant wherein R 1 and R 2 are independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 18 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -O - and -N(R 5 )2 consists of, in which each R 5 independently of each other, one substituted or unsubstituted C1-C12 -alkyl group or a substituted or unsubstituted aryl group, or R 1 and R 2 together with the phosphorus atom, form a ring or ring system; and R 3 and R 4 are selected independently from the group consisting of a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group and a substituted or unsubstituted arylalkyl group, or R 3 and R 4 together with the nitrogen atom, they form a ring or a ring system. [2] Use according to claim 1, characterized by that the ring, which R 1 and R2 together with the phosphorus atom, or the ring system that R 1 and R 2 together with the phosphorus atom, in addition to the phosphorus atom, it has at least one further heteroatom, the heteroatom being selected from the group consisting of oxygen, nitrogen and sulfur. [3] Use according to claim 1 or claim 2, characterized by , that R 1 and R 2 together with the phosphorus atom form a five- or six-membered ring to which no further ring or one or more rings are fused. [4] Use according to any of the preceding claims, characterized by , that the compound of general formula I is a compound of general formula I-A, wherein R 3 and R 4 which have meanings given in connection with the general formula I. [5] Use according to claim 1, characterized by , that R 1 and R 2are selected independently from the group consisting of a substituted or unsubstituted C1-C 12 -alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 12 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylalkyl group and a group -N(R 5 )2, wherein each R 5 independently of each other, one substituted or unsubstituted C1-C 12 -Alkyl group is, consists. [6] Use according to claim 5, characterized by , that R 1 and R 2 are each independently selected from the group consisting of a phenyl group, a phenoxy group and a -N(CH2-CH3)2 group. [7] Use according to claim 5 or claim 6, characterized by , that R 1 and R 2 are the same. [8] Use according to any of the preceding claims, characterized by , that R 3 and R 4 are independently selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl and benzyl. [9] Use according to any of the preceding claims, characterized by that it is one of the following connections N,N-Dibenzylcarbamoyloxydiphenoxyphosphine oxide, N,N-Dibenzylcarbamoyloxydiphenylphosphine oxide, N,N-Diethylcarbamoyloxydiphenoxyphosphane oxide, 10-(N,N-Diethylcarbamoyloxy)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide, 10-(N,N-Dibenzylcarbamoyloxy)-9,10-dihydro-9-0oxa-10-phosphaphenantrene-10-oxide. [10] Method for the preparation of a compound of the general formula Ivorin R 1 and R 2 are independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted C1-C 18-alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 18 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -O - and -N(R 5 )2 consists of, in which each R 5 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group or a substituted or unsubstituted aryl group, or R 1 and R 2 together with the phosphorus atom, form a ring or ring system; and R 3 and R 4are selected independently from the group consisting of a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group and a substituted or unsubstituted arylalkyl group, or R 3 and R 4 together with the nitrogen atom, form a ring or a ring system; wherein the method is the implementation of a compound of general formula II wherein R 1 , R 2 , R 3 and R 4 which have meanings given in connection with the general formula I, with oxygen or an oxygen-containing oxidizing agent to form a compound of general formula I. [11] Method for producing a compound of general formula I wherein R 1 and R 2 are independently selected from the group consisting of hydrogen, a hydroxyl group, a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted C1-C 18 -alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group, a substituted or unsubstituted arylalkyl group, -O - and -N(R 5)2 consists of, in which each R 5 independently of each other, one substituted or unsubstituted C1-C 12 -alkyl group or a substituted or unsubstituted aryl group, or R 1 and R 2 together with the phosphorus atom, form a ring or ring system; and R 3 and R 4 are selected independently from the group consisting of a substituted or unsubstituted C1-C 18 -alkyl group, a substituted or unsubstituted C2-C 18 -alkenyl group, a substituted or unsubstituted C2-C 18 -alkynyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted alkylaryl group and a substituted or unsubstituted arylalkyl group, or R 3 and R 4together with the nitrogen atom, form a ring or a ring system; wherein the method is the implementation of a compound of general formula III wherein R 1 and R 2 which have meanings given in connection with general formula I; and X Chlorine or bromine is; with a compound of general formula IV or a compound of all- common formula V wherein in the general formula IV R 3 and R 4 the meanings given in connection with general formula I and Z is selected from the group consisting of an alkali metal, an alkaline earth metal, aluminium, iron, zinc or a group -Si(R 6 )3 consists of which R 6 regardless of whether a substituted or unsubstituted C1-C cell occurs in each instance 18 -Alkyl group is; in the general formula VR 3 and R4 which have meanings given in connection with the general formula I; to a compound of the general formula I. [12] Method according to claim 11, characterized by , that the compound of general formula III reacts with the compound of general formula IV in a stoichiometric ratio of 1 : 1 to 4 at ambient temperature and ambient pressure. [13] Method according to claim 11, characterized by , that the compound of general formula III reacts with the compound of general formula V in the presence of carbon dioxide. [14] Method according to claim 13, characterized by that the carbon dioxide is supplied under pressure to a mixture of the compound of general formula III and the compound of general formula V. [15] Product comprising at least one polymer, wherein the product comprises a flame retardant, the flame retardant being a compound of general formula I as described in claims 1 to 9.