Description The invention relates to a process for manufacturing benzoxazinones and their use in a process for manufacturing triazinon-benzoxazinones.

WO 13/092856 discloses a process for the preparation of benzoxazinones comprising cycliza- tion of a respective amino compound, wherein the acid necessary for the cyciisation is dosed to the respective amino compound. However said process has several disadvantages, as purity and yield of the desired product are unsatisfying.

Hence, there is still room for improvement, specifically in view of economic aspects. One task of the invention is to provide an efficient process for manufacturing benzoxazinones of formula (I).

Surprisingly it has further been found that benzoxazinones of formula (I) can be obtained by acid-mediated cyclization of amino compounds of formula (II), wherein the amino compound of formula (II) is added to the acid.

It is therefore one object of the present invention to provide a process for manufacturing benzoxazinones of formula (I),

H

wherein

R ¹ is H or halogen;

R ² is halogen;

R ³ is H or halogen;

R ⁴ is H, Hal or NH ₂ ; and

W is O or S; characterized in that amino compounds of formula (II),

wherein R ¹ , R ² , R ³ , R ⁴ and W, are defined as in formula (I); and

R ⁵ , R ⁶ are independently of each other d-Ce-alkyl, C ₂ -Ce-alkenyl, C ₂ -Ce-alkynyl, Ci-Ce-haloalkyl, d-Ce-cyanoalkyl, Ci-C6-nitroalkyl, Ci-C ₆ -hydroxyalkyl, d-Ce- alkoxy-d-Ce-alkyl, amino-d-Ce-alkyl, (Ci-C6-alkyl)amino-CrC6-alkyl, di(d- C6-alkyl)amino-Ci-C6-alkyl, d-Ce-cycloalkyl, phenyl or benzyl, wherein the phenyl and the benzyl ring are independently of one another unsubstituted or substituted withl to 5 substituents selected from the group consisting of halo- gen, Ci-C6-alkyl or Ci-C6-alkoxy, or R ⁵ and R ⁶ together with the N atom which they are attached to, represent a saturated or aromatic 3- to 6-membered ring, optionally containing 1 to 3 additional heteroatoms from the group O, S and N, with the ring optionally being substi- tuted with 1 to 3 Ci-C6-alkyl substituents;

is added to an acid.

In a further aspect of the invention there is provided a process for manufacturing benzoxazi- nones of formula (I) from amino compounds of formula (II), wherein such amino compounds of formula (II) are prepared from nitro compounds of formula (III).

The organic moieties mentioned in the definition of the variables according to the present inven- tion, e.g. R ¹ to R ⁶ are - like the term halogen - collective terms for individual enumerations of the individual group members.

The term halogen denotes in each case fluorine, chlorine, bromine or iodine. All hydrocarbon chains, i.e. all alkyl, can be straight-chain or branched, the prefix C _n -C _m denoting in each case the possible number of carbon atoms in the group.

Examples of such meanings are:

Ci-C ₄ -alkyl: for example CH ₃ , C ₂ H ₅ , n-propyl, CH(CH ₃ ) ₂ n-butyl, CH(CH ₃ )-C ₂ H ₅ , CH ₂ - CH(CH ₃ ) ₂ and C(CH ₃ ) ₃ ;

Ci-Ce-alkyl and also the d-Ce-alkyl moieties of d-Ce-cyanoalkyl, d-Ce-nitroalkyl, d-Ce- hydroxyalkyi, d-Ce-alkyoxy-d-Ce-alkyl, amino-d-Ce-alkyl, (d-Ce-alky amino-d-Ce-alkyl and di(d-C6-alkyl)amino-d-C6-alkyl: d-C ₄ -alkyl as mentioned above, and also, for example, n- pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, n-hexyl, 1 .1 - dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- methylpentyl, 1 ,1-dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3- dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2- trimethylpropyl, 1 -ethyl-1 -methylpropyl or 1 -ethyl-2-methylpropyl, preferably methyl, ethyl, n- propyl, 1-methylethyl, n-butyl, 1 , 1-dimethylethyl, n-pentyl or n-hexyl;

Ci-C4-haloalkyl: a Ci-C4-alkyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoro- methyl, chlorodifluoromethyl, bromomethyl, iodomethyl, 2-fluoroethyl, 2-chloroethyl, 2- bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-

2.2- difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3- dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, a Ci-C3-haloalkyl radical as mentioned above, and also, for example, 1 -(fluoromethyl)-2-fluoroethyl, 1 -(chloromethyl)-2-chloroethyl, 1 - (bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl, nonafluorobutyl, 1 ,1 ,2,2,-tetrafluoroethyl and 1-trifluoromethyl-1 ,2,2,2-tetrafluoroethyl;

Ci-C6-haloalkyl: Ci-C4-haloalkyl as mentioned above, and also, for example,

5-fluoropentyl, 5-chloropentyl, 5-bromopentyl, 5-iodopentyl, undecafluoropentyl, 6-fluorohexyl, 6-chlorohexyl, 6-bromohexyl, 6-iodohexyl and dodecafluorohexyl;

C3-C6-cycloalkyl: monocyclic saturated hydrocarbons having 3 to 6 ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;

C3-C6-alkenyl: for example -propenyl, 2-propenyl, -methylethenyl, -butenyl, 2-butenyl,

3- butenyl, 1 -methyl-1 -propenyl, 2-methyl-1 -propenyl, 1 -methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl-1 -butenyl, 2-methyl-1 -butenyl, 3- methyl-1 -butenyl, 1 -methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1 -methyl-3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1 ,1 -dimethyl-2-propenyl, 1 ,2-dimethyl-

1 - propenyl, 1 ,2-dimethyl-2-propenyl, 1 -ethyl-1 -propenyl, 1 -ethyl-2-propenyl, 1 -hexenyl, 2- hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1 -methyl-1 -pentenyl, 2-methyl-1 -pentenyl, 3-methyl- 1 -pentenyl, 4-methyl-1 -pentenyl, 1 -methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl,

4- methyl-3-pentenyl, 1 -methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl- 4-pentenyl, 1 ,1 -dimethyl-2-butenyl, 1 ,1 -dimethyl-3-butenyl, 1 ,2-dimethyl-1 -butenyl, 1 ,2-dimethyl-

2- butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1 -butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl- 3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1 -butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-

3- butenyl, 3,3-dimethyl-1 -butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl-1 -butenyl, 1 -ethyl-2-butenyl, 1 - ethyl-3-butenyl, 2-ethyl-1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2- propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2-methyl-1 -propenyl and 1 -ethyl-2-methyl-2- propenyl;

- C2-C6-alkenyl: C3-C6-alkenyl as mentioned above, and also ethenyl;

C3-C6-alkynyl: for example 1 -propynyl, 2-propynyl, 1 -butynyl, 2-butynyl, 3-butynyl, 1 - methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1 -methyl-2-butynyl, 1 -methyl- 3-butynyl, 2-methyl-3-butynyl, 3-methyl-1 -butynyl, 1 ,1 -dimethyl-2-propynyl, 1 -ethyl-2-propynyl, 1 -hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2-pentynyl, 1 -methyl-3- pentynyl, 1 -methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1 -pentynyl, 3- methyl-4-pentynyl, 4-methyl-1 -pentynyl, 4-methyl-2-pentynyl, 1 ,1-dimethyl-2-butynyl, 1 ,1- dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1 -butynyl, 1 - ethyl-2-butynyl, 1 -ethyl-3-butynyl, 2-ethyl-3-butynyl and 1 -ethyl-1 -methyl-2-propynyl;

C2-C6-alkynyl: C3-C6-alkynyl as mentioned above and also ethynyl;

Ci-C4-alkoxy: for example methoxy, ethoxy, propoxy, 1 -methylethoxy butoxy,

1 -methylpropoxy, 2-methylpropoxy and 1 ,1 -dimethylethoxy;

Ci-C6-alkoxy: Ci-C4-alkoxy as mentioned above, and also, for example, pentoxy, 1 - methylbutoxy, 2-methylbutoxy, 3-methoxylbutoxy, 1 ,1 -dimethylpropoxy, 1 ,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1 -ethylpropoxy, hexoxy, 1 -methylpentoxy, 2-methylpentoxy, 3- methylpentoxy, 4-methylpentoxy, 1 ,1-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1 ,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1 ,1 ,2- trimethylpropoxy, 1 ,2,2-trimethylpropoxy, 1 -ethyl-1-methylpropoxy and 1 -ethyl-2-methylpropoxy.

(Ci-C4-alkyl)amino: for example methylamino, ethylamino, propylamino, 1-methylethyl- amino, butylamino, 1-methylpropylamino, 2-methylpropylamino or 1 , 1-dimethylethylamino;

(Ci-C6-alkyl)amino and also the (Ci-C6-alkyl)amino moieties of (Ci-C6-alkyl)amino-Ci-C6- alkyl: (Ci-C4-alkylamino) as mentioned above, and also, for example, pentylamino, 1 - methylbutylamino, 2-methylbutylamino, 3-methylbutylamino, 2,2-dimethylpropylamino, 1 -ethyl- propylamino, hexylamino, 1 ,1 -dimethylpropylamino, 1 ,2-dimethylpropylamino, 1 -methyl- pentylamino, 2-methylpentylamino, 3-methylpentylamino, 4-methylpentylamino, 1 ,1 -dimethyl- butylamino, 1 ,2-dimethylbutylamino, 1 ,3-dimethylbutylamino, 2,2-dimethylbutylamino, 2,3- dimethylbutyl-amino 3,3-dimethylbutylamino, 1 -ethylbutylamino, 2-ethylbutylamino, 1 ,1 ,2- trimethylpropylamino, 1 ,2,2-trimethyl-propylamino, 1 -ethyl-1 -methylpropylamino or 1 -ethyl-2- methylpropylamino;

di(Ci-C4-alkyl)amino: for example N,N-dimethylamino, Ν,Ν-diethylamino, N,N-di(1 - methylethyl)amino, N,N-dipropylamino, Ν,Ν-dibutylamino, N,N-di(1 -methylpropyl)amino, N,N- di(2-methylpropyl)amino, N,N-di(1 ,1 -dimethylethyl)amino, N-ethyl-N-methylamino, N-methyl-N- propylamino, N-methyl-N-(1-methylethyl)amino, N-butyl-N-methylamino, N-methyl-N-(1- methylpropyl)amino, N-methyl-N-(2-methylpropyl)amino, N-(1 ,1 -dimethylethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1 -methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1 - methylpropyl)amino, N-ethyl-N-(2-methylpropyl)amino, N-ethyl-N-(1 ,1 -dimethylethyl)amino, N- (l -methylethyl)-N-propylamino, N-butyl-N-propylamino, N-(1 -methylpropyl)-N-propylamino, N-(2- methylpropyl)-N-propylamino, N-(1 ,1 -dimethylethyl)-N-propylamino, N-butyl-N-(1 - methylethyl)amino, N-(1 -methylethyl)-N-(1 -methylpropyl)amino, N-(1 -methylethyl)-N-(2-methyl- propyl)amino, N-(1 ,1 -dimethylethyl)-N-(1 -methylethyl)amino, N-butyl-N-(1 -methylpropyl)amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1 ,1 -dimethylethyl)amino, N-(1 -methylpropyl)-N-(2- methylpropyl)amino, N-(1 ,1 -dimethylethyl)-N-(1 -methylpropyl)amino or N-(1 ,1 -dimethylethyl)-N- (2-methylpropyl)amino; di(Ci-C6-alkyl)amino and also the di(Ci-C6-alkyl)amino moieties of di(Ci-C6-alkyl)amino- Ci-C6-alkyl: di(Ci-C4-alkyl)amino as mentioned above, and also, for example, N-methyl-N- pentylamino, N-methyl-N-(1 -methylbutyl)amino, N-methyl-N-(2-methylbutyl)amino, N-methyl-N- (3-methylbutyl)amino, N-methyl-N-(2,2-dimethylpropyl)amino, N-methyl-N-(1 -ethylpropyl)amino, N-methyl-N-hexylamino, N-methyl-N-(1 ,1 -dimethylpropyl)amino, N-methyl-N-(1 ,2- dimethylpropyl)amino, N-methyl-N-(1 -methylpentyl)amino, N-methyl-N-(2-methylpentyl)amino, N-methyl-N-(3-methylpentyl)amino, N-methyl-N-(4-methylpentyl)amino, N-methyl-N-(1 ,1 - dimethylbutyl)amino, N-methyl-N-(1 ,2-dimethylbutyl)amino, N-methyl-N-(1 ,3- dimethylbutyl)amino, N-methyl-N-(2,2-dimethylbutyl)amino, N-methyl-N-(2,3- dimethylbutyl)amino, N-methyl-N-(3,3-dimethylbutyl)amino, N-methyl-N- (l -ethylbutyl)amino, N- methyl-N-(2-ethylbutyl)amino, N-methyl-N-(1 ,1 ,2-trimethylpropyl)amino, N-methyl-N- (1 ,2,2- trimethylpropyl)amino, N-methyl-N-(1 -ethyl-1 -methylpropyl)amino, N-methyl-N- (1 -ethyl-2- methylpropyl)amino, N-ethyl-N-pentylamino, N-ethyl-N-(1 -methylbutyl)amino, N-ethyl-N-(2- methylbutyl)amino, N-ethyl-N-(3-methylbutyl)amino, N-ethyl-N-(2,2-dimethylpropyl)amino, N- ethyl-N-(1 -ethylpropyl)amino, N-ethyl-N-hexylamino, N-ethyl-N-(1 ,1 -dimethylpropyl)amino, N- ethyl-N-(1 ,2-dimethylpropyl)amino, N-ethyl-N-(1 -methylpentyl)amino, N-ethyl-N-(2-methyl- pentyl)amino, N-ethyl-N-(3-methylpentyl)amino, N-ethyl-N-(4-methylpentyl)amino, N-ethyl-N- (1 ,1 -dimethylbutyl)amino, N-ethyl-N-(1 ,2-dimethylbutyl)amino, N-ethyl-N-(1 ,3- dimethylbutyl)amino, N-ethyl-N-(2,2-dimethylbutyl)amino, N-ethyl-N-(2,3-dimethylbutyl)amino, N-ethyl-N-(3,3-dimethylbutyl)amino, N-ethyl-N-(1 -ethylbutyl)amino, N-ethyl-N-(2- ethylbutyl)amino, N-ethyl-N-(1 ,1 ,2-trimethylpropyl)amino, N-ethyl-N-(1 ,2,2- trimethylpropyl)amino, N-ethyl-N-(1 -ethyl-1 -methylpropyl)amino, N-ethyl-N-(1 -ethyl-2- methylpropyl)amino, N-propyl-N-pentylamino, N-butyl-N-pentylamino, Ν,Ν-dipentylamino, N- propyl-N-hexylamino, N-butyl-N-hexylamino, N-pentyl-N-hexylamino or N,N-dihexylamino;

- saturated or aromatic 3- to 6-membered ring optionally containing 1 to 3 additional heteroatoms selected from the group O, S and N:

a monocyclic, saturated or aromatic cycle having three to six ring members which comprises apart from one nitrogen atom and carbon atoms optionally additionally one to three heteroatoms selected from the group O, S and N, for example:

1-aziridinyl, 1-azetidinyl; 1-pyrrolidinyl, 2-isothiazolidinyl, 2-isothiazolidinyl, 1-pyrazolidinyl, 3- oxazolidinyl, 3-thiazolidinyl, 1 -imidazolidinyl, 1 ,2,4-triazolidin-1 -yl, 1 ,2,4-oxadiazolidin-2-yl, 1 ,2,4- oxadiazolidin-4-yl, 1 ,2,4-thiadiazolidin-2-yl, 1 ,2,4-thiadiazolidin-4-yl; 1 -pyrrolyl, 1 -pyrazolyl, 1 - imidazolyl, 1 ,2,3-triazol-1 -yl, 1 ,2,4-triazol-1 -yl, 1 -tetrazolyl; 1 -piperidinyl, 1 -hexahydropyridazinyl, 1 -hexahydropyrimidinyl, 1 -piperazinyl, 1 ,3,5-hexahydrotriazin-1 -yl, 1 ,2,4-hexahydrotriazin-1 -yl, tetrahydro-1 ,3-oxazin-1 -yl, 1 -morpholinyl.

The preferred embodiments of the invention mentioned herein below have to be understood as being preferred either independently from each other or in combination with one another. According to a preferred embodiment of the invention preference is also given to the preparation of those benzoxazinones of formula (I), wherein the variables, either independently of one another or in combination with one another, have the following meanings: R ¹ is preferably H or F; particularly preferred H;

is also preferably halogen, particularly preferred F or CI, especially preferred F;

R ² is preferably CI or F, particularly preferred F; is preferably H, CI or F, particularly preferred H or F, especially preferred H;

is also preferably halogen, particularly preferred F or CI, especially preferred F; is preferably H or halogen, particularly preferred H;

is also preferably halogen or NH ₂ , particularly preferred halogen;

is also preferred H or NH ₂ , particularly preferred ΝΗ ₂ ;

W is preferably O,

is also preferably S.

Particular preference is also given to the preparation of benzoxazinones of formula (la), which correspond to benzoxazinones of formula (I) wherein R ³ is F:

I

Particular preference is also given to the preparation of benzoxazinones of formula (la.1 ), which correspond to benzoxazinones of formula (I) wherein R ³ is F and R ⁴ is NH2:

Particular preference is also given to the preparation of benzoxazinones of formula (la.2), which correspond to benzoxazinones of formula (I) wherein R ² and R ³ are F:

Particular preference is also given to the preparation of the benzoxazinone of formula (la.1 .1 ), which corresponds to benzoxazinones of formula (I) wherein R ¹ , R ² and R ³ are F, R ⁴ is H2 and W is O:

With respect to the variables within the amino compound of formula (II), the particularly preferred embodiments correspond, either independently of one another or in combination with one another, to those of the variables of R ¹ , R ² , R ³ , R ⁴ and W of formula (I), or have, either independently of one another or in combination with one another, the following meanings:

R ⁵ and R ⁶ preferably are independently of each other Ci-C6-alkyl, Ci-C6-cyanoalkyl, C1-C6- hydroxyalkyl, Ci-C6-alkoxy-Ci-C6-alkyl, C3-C6-cycloalkyl, phenyl or benzyl,

wherein the phenyl and the benzyl ring are independently of one another unsubsti- tuted or substituted with 1 to 3 substituents selected from the group consisting of halogen, Ci-C6-alkyl or Ci-C6-alkoxy,

or R ⁵ and R ⁶ together with the N atom which they are attached to, represent a saturated or aromatic 5- to 6-membered ring, optionally containing 1 additional heteroatom from the group O and N, with the ring optionally being substituted with 1 to 2 Ci-C6-alkyl substituents; particularly preferred are independently of each other Ci-C ₄ -alkyl, Ci-C4-hydroxyalkyl, Ci- C6-alkoxy-Ci-C4-alkyl or benzyl,

wherein the benzyl ring is unsubstituted or substituted by 1 to 3 substituents selected from the group consisting of halogen, Ci-C ₄ -alkyl or Ci-C ₄ -alkoxy,

especially preferred the benzyl ring is unsubstituted,

or R ⁵ and R ⁶ together with the N atom which they are attached to, represent a saturated 5- to 6-membered ring, optionally containing 1 additional oxygen atom, with the ring optional- ly being substituted with 1 to 2 Ci-C6-alkyl substituents; also particularly preferred are independently of one another Ci-C6-alkyl. In the process according to the invention, amino compounds of formula (II) are added to an acid to obtain the benzoxazinones of formula (I):

wherein the substituents are as herein defined.

The process according to the invention is generally carried out at a temperature in the range of from 0 °C to the boiling point of the solvents, preferably in the range from 25 to 80 °C, especially preferred in the range from 40 to 65 °C.

Examples for suitable acids are organic acids or inorganic acids.

Examples of suitable organic acids are formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, succinic acid, adipic acid, maleic acid, fumaric acid, citric acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, bromoacetic acid, trifluoroacetic acid, benzoic acid, ni- trobenzoic acid, methanesulfonic acid, trifluoromethanesulfonic acid (triflic acid), bis(trifluoro- methane)sulfonimide (triflimide), camphorsulfonic acid, benzenesulfonic acid, para-toluene- sulfonic acid, nitrobenzenesulfonic acid or dinitrobenzenesulfonic acid.

Examples of suitable inorganic acids are hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, tetrafluoroboric acid, hex- afluorophosphoric acid or hexafluorosilicic acid.

According to a preferred embodiment of the invention, the concentration of the acid is below 50%, preferably below 30 %.

According to another preferred embodiment of the invention, the concentration of the acid is from 3 to 50%, preferably from 10 to 30 %. Preferred acids are acetic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, sulfuric acid and nitric acid.

Particularly preferred acids are hydrochloric acid, sulfuric acid and acetic acid.

Especially preferred acids are hydrochloric acid and sulfuric acid.

A more preferred acid is sulfuric acid. According to a preferred embodiment of the invention, the concentration of the sulphuric acid is below 50%, preferably below 30 %.

According to another preferred embodiment of the invention, the concentration of the sulphuric acid is from 3 to 50%, preferably from 10 to 30 %.

The term acid as used herein also includes mixtures of two or more, preferably two of the above compounds. Particular preference is given to the use of one acid. Accordingly, in a particularly preferred embodiment one acid is employed.

The molar ratio of the amino compound of formula (II) to the acid is generally in the range of 1 :0.5 to 1 :10, preferably 1 :1 to 1 :2, more preferably 1 :1.

Preferably the process according to the invention is carried out in a solvent.

Examples of suitable solvents are water, alcohols such as methanol, ethanol, 1 -propanol, 2- propanol, 1 -butanol, 2-butanol, iso-butanol, tert-butanol, 2-ethyl-hexanol, hexafluoroisopropanol; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, cymene, xylenes, mesitylene, benzotrifluoride; esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate; ethers such as di-n-butyl ether, tert-butyl methyl ether (TBME), tetrahydrofuran (THF), 1 ,4- dioxane, 1 ,2-dimethoxyethane; aliphatic hydrocarbons such as hexanes, cyclohexane; dipolar aprotic solvents such as Ν,Ν-dimethylformamide (DMF), Ν,Ν-dibutylformamide, N,N- dimethylacetamide (DMAC), 1 -methyl-2-pyrrolidinone (NMP), 1 ,3-dimethyl-2-imidazolidinone (DMI), Ν,Ν'-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO), sulfolane.

Preferred solvents are alcohols as mentioned above, and water.

Preferred solvents include methanol, ethanol, isopropanol, toluene, xylenes and water.

More preferred solvents include methanol, toluene and water. More preferred solvents are methanol and toluene.

The term solvent as used herein also includes mixtures of two or more of the above compounds.

Particular preference is given to the use of methanol/toluene/water mixtures.

Also particular preference is given to the use of methanol/toluene mixtures.

In a preferred embodiment the acid and a solvent are pre-charged in the reaction vessel and then the mixture is heated to a definite temperature, before the amino compounds of formula (II) are added.

In another preferred embodiment the acid and a solvent are pre-charged in the reaction vessel and then a solution of the amino compounds of formula (II) in a solvent are dosed to the pre- charged catalyst/solvent mixture in that way, that the benzoxazinones of formula (I) are formed immediately.

In another preferred embodiment the acid and a solvent are pre-charged in the reaction vessel, then a solution of the amino compounds of formula (II) in a solvent are dosed to the pre-charged acid/solvent mixture in that way, that the benzoxazinones of formula (I) are formed immediately and the reaction temperature can be kept constant in a desired range.

After completion or partial completion of the cyclization reaction, the respective mixture can be worked up by means of standard techniques. Examples thereof include extraction, filtration, aqueous work-up, distilling off solvents and/or other volatile compounds. These methods can also be combined with each other. The benzoxazinones of formula (I) can also be used without further purification or can be purified using standard techniques, for example precipitation, recrystallization or column chromatography.

According to one embodiment of the invention, after completion or partial completion of the cy- clization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably 3 to 7, more preferably 4 to 5.

According to one embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably a pH from 3 to 7, more preferably from 4 to 5. According to another embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to a pH of 4.

In a further embodiment, the benzoxazinones of formula (I) are isolated by precipitation.

The precipitated benzoxazinones of formula (I) can be isolated by filtration.

According to one embodiment of the invention, the benzoxazinones of formula (I) precipitate upon cooling, preferably to a temperature in the range of from 0 to 30 °C. According to another embodiment of the invention, the benzoxazinones of formula (I) are precipitated by adding water to the reaction mixture.

According to another embodiment of the invention, the benzoxazinones of formula (I) precipitate upon cooling, preferably to a temperature in the range of from 0 to 30 °C, and adding water.

According to another embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably 3 to 7, more preferably 4 to 5. The benzoxazinones of formula (I) precipitate upon cooling, preferably to a temperature in the range of from 0 to 30 °C and/or adding water.

According to another embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably 3 to 7, more preferably 4 to 5, and the reaction mixture is cooled, preferably to a temperature in the range of from 0 to 30 °C, to precipitate the benzoxazinones of formula (I).

According to another embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably 3 to 7, more preferably 4 to 5, and water is added to the reaction mixture to precipitate the benzoxa- zinones of formula (I).

According to another embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably 3 to 7, more preferably 4 to 5, water is added to the reaction mixture, and the reaction mixture is cooled, preferably to a temperature in the range of from 0 to 30 °C, to precipitate the benzoxazinones of formula (I).

According to another embodiment of the invention, after completion or partial completion of the cyclization reaction, the pH of the reaction mixture is adjusted to slightly acidic, preferably 3 to 7, more preferably 4 to 5. After addition of water the benzoxazinones of formula (I) precipitate in a temperature range from 0 to 30 °C. Such embodiment is preferred.

The benzoxazinones of formula (I) are suitable intermediates for the synthesis of triazinon- benzoxazinones, e.g. as disclosed in WO 2013/092856.

Amino compounds of formula (I I) can prepared by known methods, e.g. by reacting nitro compounds of formula (II I) with a reducing agent to obtain the amino compound of formula (I I),

wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ - R ⁶ and W are as defined above; and

R ^A is H, Hal, NH ₂ or N0 ₂ .

Amino compounds of formula (I I) can also be prepared by adding a nitro compound of formula (I I I) to a reducing agent :

reducing agent

( I I )

wherein the substituents are as herein defined.

The reduction of the nitro compounds of formula (II I) is generally carried out at a temperature in the range of from 0 °C to the boiling point of the solvents, preferably 20 to 80 °C, especially preferred in the range from 35 to 65 °C.

Examples of suitable reducing agents and conditions are known from the literature and can be found inter alia in Advanced Organic Chemistry (ed. J. March), 4 ^th edition, Wiley-lnterscience, NY 1992, p.1216 ff; or Organikum, 22 ^nd edition, Wiley-VCH, Weinheim 2004, p. 626 ff. Examples for reducing agents are molecular hydrogen, hydrazine, formic acid, ammonium formate, borane or borohydrides in combination with a homogeneous or heterogeneous catalyst, for example selected from metal salts of nickel, palladium, platinum, cobalt, rhodium, iridium, ruthenium or copper.

Specific examples for catalysts are palladium on charcoal, palladium on alumina, palladium on BaS0 ₄ , platinum on charcoal, platinum on alumina, platinum(IV) oxide, Raney nickel, rhodium on alumina, ruthenium on alumina. Further examples of suitable reducing agents are metals in their elemental form such as magnesium, iron, zinc, tin or metal salts such as tin(ll) chloride in combination with an acid such as hydrochloric or acetic acid.

Further examples of suitable reducing agents are sulfur compounds like sodium hydrosulfite, rongalite, sodium sulfide, sodium hydrogen sulfide and ammonium polysulfide.

In a preferred embodiment of the process according to the invention the reducing agent is molecular hydrogen in combination with a homogeneous or heterogeneous hydrogenation catalyst.

Examples for hydrogenation catalysts are catalyst selected from the group consisting of metal salts of nickel, palladium, platinum, cobalt, rhodium, iridium, ruthenium or copper.

Specific examples for hydrogenation catalysts include palladium on charcoal, palladium on alu- mina, palladium on BaS0 ₄ , platinum on charcoal, platinum on alumina, platinum(IV) oxide, Raney nickel, rhodium on alumina, ruthenium on alumina.

Preferred reducing agents are molecular hydrogen in combination with palladium on charcoal, palladium on alumina, palladium on BaS0 ₄ , molecular hydrogen in combination with platinum on charcoal, platinum on alumina.

Especially preferred reducing agents are molecular hydrogen in combination with palladium on charcoal or platinum on charcoal. A more preferred reducing agent is molecular hydrogen in combination with palladium on charcoal.

Also a more preferred reducing agent is molecular hydrogen in combination with platinum on charcoal. The term reducing agent as used herein also includes mixtures of two or more, preferably two of the above compounds. Particular preference is given to the use of one reducing agent.

Accordingly, in a particularly preferred embodiment one reducing agent is employed in the pro- cess according to the invention.

The molar ratio of the nitro compound of formula (III) to the reducing agent is generally in the range of 1 :2 to 1 :15, preferably 1 :2.5 to 1 :10, more preferably 1 :3 to 1 :6.

In a preferred embodiment the reducing agent and the solvent are pre-charged in the reaction vessel and then the mixture is heated to a definite temperature, before the nitro compound of formula (III) is added.

In another preferred embodiment the reducing agent and the solvent are pre-charged in the reaction vessel and then the nitro compound of formula (III) is dosed to the pre-charged catalyst/solvent mixture in such way, that the nitro compound of formula (III) is reduced immediately, and thus the stationary concentration of nitro compound of formula (III) in the reaction mixture is very low.

In another preferred embodiment with the reducing agent being molecular hydrogen in combination with a catalyst, the catalyst and the solvent are pre-charged in the reaction vessel, the mix- ture is heated to a definite temperature, and then pressurized with hydrogen under stirring before the nitro compound of formula (III) is added.

In another preferred embodiment with the reducing agent being molecular hydrogen in combination with a catalyst, the catalyst and the solvent are pre-charged in the reaction vessel and then a solution of the nitro compound of formula (III) in a solvent is dosed to the pre-charged catalyst/solution mixture in that way, that the nitro compound of formula (III) is reduced immediately.

In another preferred embodiment with the reducing agent being molecular hydrogen in combination with a catalyst, the catalyst and the solvent are pre-charged in the reaction vessel and then a solution of the nitro compound of formula (III) in a solvent is dosed to the pre-charged catalyst/solution mixture in such way, that the nitro compound of formula (III) is reduced immediately, and thus the stationary concentration of nitro compound of formula (III) in the reaction mixture is very low. In another preferred embodiment with the reducing agent being molecular hydrogen in combination with a catalyst, the catalyst and the solvent are pre-charged in the reaction vessel and then a solution of the nitro compound of formula (III) in a solvent is dosed to the pre-charged catalyst/solvent mixture in that way, that the nitro compound of formula (III) is reduced immediately and the reaction temperature can be kept constant in a desired range.

In another preferred embodiment with the reducing agent being molecular hydrogen in combination with a catalyst, first the mixture of the catalyst and a solvent are stirred at a temperature in the range of from 20 to 80 °C, preferably 40 to 60 °C, in the presence of hydrogen at a pressure in the range of from 0 to 20 bar, preferably 0 to 10 bar; and then the nitro compound of formula (III) is added.

The process according to the invention is carried out under an elevated pressure of up to 20 bar, preferably up to 10 bar.

Preferably, the reduction of the nitro compounds of formula (III) is carried out in a solvent.

Examples of suitable solvents are water, alcohols such as methanol, ethanol, 1 -propanol, 2- propanol, 1-butanol, 2-butanol, iso-butanol, tert-butanol, 2-ethyl-hexanol, hexafluoroisopropanol; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, cymene, xylenes, mesitylene, benzotrifluoride; esters such as methyl acetate, ethyl acetate, n-butyl acetate, isobutyl acetate; ethers such as di-n-butyl ether, tert-butyl methyl ether (TBME), tetrahydrofuran (THF), 1 ,4- dioxane, 1 ,2-dimethoxyethane; aliphatic hydrocarbons such as hexanes, cyclohexane; dipolar aprotic solvents such as Ν,Ν-dimethylformamide (DMF), Ν,Ν-dibutylformamide, N,N- dimethylacetamide (DMAC), 1 -methyl-2-pyrrolidinone (NMP), 1 ,3-dimethyl-2-imidazolidinone (DMI), Ν,Ν'-dimethylpropylene urea (DMPU), dimethyl sulfoxide (DMSO), sulfolane. Preferred solvents include methanol, toluene and xylenes.

More preferred solvents include methanol and toluene.

The term solvent as used herein also includes mixtures of two or more of the above solvents. Preference is given to the use of methanol/toluene mixtures or methanol/xylenes mixtures. Particular preference is given to the use of methanol/toluene mixtures.

After completion or partial completion of the reaction, the respective mixture can be worked up by means of standard techniques. Examples thereof include extraction, filtration, aqueous work- up, distilling off solvents and/or other volatile compounds. These methods can also be combined with each other.

In a preferred embodiment the hydrogen source is removed and the catalyst is filtered off.

In another preferred embodiment the reaction mixture is brought to room temperature and the catalyst is filtered off. The solvent is partly or completely distilled off.

The product precipitates upon cooling, preferably to a temperature in the range of from 0 to 30 °C and/or adding water. The precipitated amino compound of formula (I) can be isolated by filtration.

The amino compounds of formula (II) are suitable intermediates for the synthesis of benzoxazi- nones of formula (I).

Accordingly, in a further preferred embodiment of the invention benzoxazinones of formula (I) are prepared by

(i) reacting nitro compounds of formula (III)

wherein R ¹ , R ² , R ³ , R ⁵ - R ⁶ and W are as defined above; and R ^A is H, Hal, NH ₂ or N0 ₂ ;

with a reducing agent to obtain amino compounds of formula (II); and

(ii) adding such amino compounds of formula (II) to an acid.

In another preferred embodiment of the invention benzoxazinones of formula (I) are prepared by

(i) adding nitro compounds of formula (III) to a reducing agent to obtain amino compounds of formula (II); and

(ii) adding such amino compounds of formula (II) to an acid.

In one embodiment the amino compounds of formula (II) are isolated prior to being used in step (ii).

In another embodiment the amino compounds of formula (II) are not isolated, and the reaction mixture obtained in step (i) is directly used in step (ii).

Such embodiment is preferred. In another embodiment the amino compounds of formula (II) are not isolated, and the reaction mixture obtained in step (i) is directly used in step (ii) under inert conditions, especially under exclusion of oxygen.

Such embodiment is especially preferred.

According to another embodiment of the invention, the catalyst is filtered off, and the filtrate containing the amino compound of formula (II) used in one or more subsequent reaction step(s). In another preferred embodiment the catalyst is filtered off and the amino compound of formula (II) is not isolated, but the filtrate containing such amino compound of formula (II) is dosed immediately in another reactor to be used in one or more subsequent reaction step(s).

Preferably such filtration is conducted under inert conditions, especially under exclusion of oxy- gen.

According to another embodiment of the invention, the catalyst is filtered of and recycled.

In another particular embodiment, the solvent is not exchanged between carrying out steps (i) and (ii).

In another preferred embodiment with the reducing agent being molecular hydrogen in combination with a catalyst, a mixture of nitro compounds of formula (III), the catalyst, and a solvent are stirred at a temperature in the range of from 20 to 60 °C, preferably 40 to 60 °C, in the presence of hydrogen at a pressure in the range of from 0 to 20 bar, preferably 0 to 10 bar. After completion or partial completion of step (i), the hydrogen source is removed. The catalyst is optionally filtered off, and the filtrate is subsequently used in step (ii), i.e. is added to the acid. Such reaction mixture is then stirred at a temperature in the range of from 20 to 65 °C, preferably 40 to 65 °C, for 0.5 to 5 h, preferably 0.5 to 2 h.

In another embodiment the reaction mixture is brought to room temperature and the catalyst is filtered off. Then the filtrate is subsequently used in step (ii), i.e. is added to the acid.

In another embodiment the catalyst is filtered off from the reaction mixture in a temperature range of 50 to 60 °C. The filter cake is washed with methanol up to three times. Then the filtrate is subsequently used in step (ii), i.e. is added to the acid. In another embodiment the catalyst is filtered off from the reaction mixture and the filtrate is brought to room temperature. Then the filtrate is subsequently used in step (ii), i.e. is added to the acid.

The nitro compounds of formula (III) can be prepared by known methods, e.g. as described in WO 2013/092856.

The invention is illustrated by the following examples without being limited thereto or thereby. 1 . Preparation of benzoxazinones of formula (I)

Synthesis of 6-amino-2,2,7-trifluoro-4H-benzo-[1 ,4]-oxazin-3-one from 2,2-difluoro-2-(2,4-dinitro- 5-fluoro-phenoxy)]-N,N-dimethyl-acetamide

Example 1.1 :

29.45 g (0.0005 mol) Pt on charcoal (0.8% Pt in dry catalyst; 58.6% water content) and 827.7 g methanol were placed in the reaction vessel.

The mixture was heated to 40°C and then pressurized with 2 bar H2 under vigorous stirring. A solution of 323.2 g (1.00 mol) 2,2-difluoro-2-(2,4-dinitro-5-fluoro-phenoxy)-N,N-dimethyl- acetamide in 1292.8 g toluene was dosed within 3 hours. The transfer pipe was purged with 82.9 g toluene.

The temperature of the reaction mixture was held constantly at 39 - 41 °C by cooling. After completion of the reaction the pressure is released and the catalyst is filtered off through a pressure filter (1 bar nitrogen overpressure).

Then the filtrate (containing the respective amino compound (III) intermediate) was piped into a second reactor and there at 60°C dosed to 376.0 g (1.15 mol) pre-charged sulfuric acid (30% in water).

The remaining catalyst was washed with 200 g methanol, which was then filled into the hydro- genation reactor, pressed through the filter cake, and then also piped into the second reactor containing the sulfuric acid reaction mixture. Such reaction mixture was stirred for additional 50 minutes at 60°C. Then NaOH (25% in H2O) was added to the mixture to adjust the pH from 1 .8 to 4. Afterwards 1652.9 g water was added and the suspension was cooled to 15°C. The precipitated solid was filtered off, washed three times with 142.9 g water in each case and dried under reduced pressure at 50°C resulting in 21 1.4 g of the desired product having 98% purity determined by quanti- tative HPLC method as described below (t.R = 12.73 min; corresponding chemical yield 95%).

Chromatographic conditions:

Column: Symmetry C18 5 μηη 250 x 4.6 mm from Waters

Wavelength: 210 nm

Eluent: gradient of A (0.1 % by volume of H3PO4 in H ₂ 0) and B (0.1 % by volume of

H3PO4 in acetonitrile); starting with 10% B, then B rising from 10% to 50% within 10 min, then B rising from 50% to 90% within 20 min, then back to 10% B within 2 min, then 8 min 10% B

Flow rate: 1 ml/min

Pressure: approx. 160 bar

¹ H NMR (DMSO-de, 500 MHz): δ (ppm) = 11 .9 (bs, 1 H); 7.15 (d, 1 H); 6.55 (d, 1 H); 5.28 (bs, 2 H).

Comparative Example 1 .2 (WO 13/092856, example 1 .1 )

To a solution of 2,2-difluoro-2-(2,4-dinitro-5-fluoro-phenoxy)-/V,/V-dimethyl -acetamide (60.0 g, 186 mmol) in toluene (432 g) was added Pd on charcoal (5% Pd, 50% water content,

1 .1 mmol). Thereafter methanol (492 g) was added and the mixture was stirred under an atmosphere of hydrogen (over pressure 0.1 bar) at 45 °C for 2 h. After completion of the reaction the pressure was released, concentrated HCI (36.5%, 22 g, 220 mmol) added and the reaction mixture heated to reflux for further 1 h. The catalyst was filtered off, the pH adjusted with NaOH to 9 and the methanol distilled off under reduced pressure. After addition of water (200 g) and stirring for 1 h the precipitate was filtered off, washed twice with water (100 g) and dried at 50 °C under reduced pressure. The product was obtained as a tan solid (38.9 g, 90% pure by NMR, 160 mmol, 86% yield).

¹ H NMR (DMSO-de, 500 MHz): δ (ppm) = 1 1.9 (bs, 1 H); 7.15 (d, J = 1 1.0 Hz, 1 H); 6.55 (d, J = 8.5 Hz, 1 H); 5.28 (bs, 2 H).

1 ³ C NMR (DMSO-de, 125 MHz): δ (ppm) = 153.7 (t, J = 38 Hz); 146.1 (d, J = 235 Hz); 133.9 (d, J = 15 Hz); 127.3 (d, J = 1 1 Hz); 120.9 (d, J = 3 Hz); 1 13.1 (t, J = 260 Hz); 104.9 (d, J = 24 Hz); 102.4 (d, J = 5 Hz).

2. Preparation of amino compounds of formula (II) Synthesis of 2,2-Difluoro-2-(2,4-diamino-5-fluoro-phenoxy)-N,N-dimethyl-a cetamide

Example 2.1 :

29.8 g (0.007 mol) Pd/C (5% Pd in dry catalyst; 50% water content) and 579.4 g methanol were placed in the reaction vessel. The mixture was heated to 40°C and then pressurized with 2 bar H2 under vigorous stirring.

A solution of 226.3 g (0.7 mol) 2,2-difluoro-2-(2,4-dinitro-5-fluoro-phenoxy)-N,N-dimethyl- acetamide in 895.7 g toluene was dosed within 3 hours. The transfer pipe was purged with 58 g toluene.

The temperature of the reaction mixture was held constantly at 39 - 41 °C with cooling.

After completion of the reaction the pressure was released and the catalyst was filtered off through a pressure filter (1 bar nitrogen overpressure). The remaining catalyst was washed with 140 g methanol. The filtrate and wash methanol were combined and evaporated to dryness.

193.7 g of the desired product have been obtained having 90% purity determined by quantitative HPLC method as described below (t.R = 8.02 min; corresponding chemical yield 94% yield). Chromatographic conditions:

Column: Symmetry C18 5 μηη 250 x 4.6 mm from Waters

Wavelength: 210 nm

Eluent: gradient of A (0.1 % by volume of H3PO4 in H ₂ 0) and B (0.1 % by volume of

H3PO4 in acetonitrile); starting with 10% B, then B rising from 10% to 50% within 10 min, then B rising from 50% to 90% within 20 min, then back to

10% B within 2 min, then 8 min 10% B

Flow rate: 1 ml/min

Pressure: approx. 160 bar

¹ H NMR (DMSO-d ₆ , 400 MHz): δ (ppm) = 6.79 (d, 1 H); 6.16 (d, 1 H); 4.95 (bs, 2 H); 4.60 (bs, 2 H); 3.19 (s, 3 H); 2.95 (s, 3 H).

Comparative example 1.2 (WO 13/092856, example 3.1 ):

To a solution of 2,2-difluoro-2-(2,4-dinitro-5-fluoro-phenoxy)-A/,A/-dimethyl -acetamide (22.0 g, 68.1 mmol) in toluene (200 g) Pd/C (10% Pd, dry catalyst, 0.7 g, 0.7 mmol) was added. Thereafter, methanol (80 g) was added and the mixture was stirred under an atmosphere of hydrogen (pressure of 0.1 bar) at 45 °C for 90 min. After completion of the reaction the pressure was released, the catalyst was filtered off and the filtrate was evaporated to dryness.

The product (17.3 g, 84% pure by NMR, 55.2 mmol, 81 % yield) was obtained as an off-white solid. If desired, the purity can be increased by chromatography (S1O2, cyclohexane/EtOAc mix- tures).

H NMR (DMSO-de, 500 MHz): δ (ppm) = 6.79 (d, J = 1 1.0 Hz, 1 H); 6.16 (d, J = 8.5 Hz, 1 H); 4.95 (bs, 2 H); 4.60 (bs, 2 H); 3.19 (s, 3 H); 2.96 (bs, 3 H).

3C NMR (DMSO-de, 125 MHz): δ (ppm) = 158.3 (t, J = 35 Hz); 141.7 (d, J = 278 Hz); 137.6; 134.9 (d, J = 14 Hz); 123.9 (d, J = 9 Hz); 1 15.8 (t, J = 272 Hz); 109.2 (d, J = 22 Hz); 102.0 (d, J = 4 Hz); 36.9; 36.2.