DE3609140A1 - Liquid-crystalline dihydroazines - Google Patents

Abstract

Dihydroazines of the formula I, R<1>-A<1>-Z<1>-A<2>-R<2> in which R<1>, R<2>, A<1>, A<2> and Z<1> have the meanings given in Patent Claim 1, can be used as components of liquid-crystalline phases.

Description

The main application contains 5,6-dihydroazines of the formula I. described

R ¹ -A ¹ -Z ¹ -A ² -R ² (I)

wherein
R ¹ and R ² alkyl with 1-15 C atoms, wherein also one or two non-adjacent CH ₂ groups by -O-, -CO-, -O-CO-, -CO-O- and / or -CH = CH- can be replaced, one of the radicals R ¹ and R ² also H, F, Cl, Br, CN, R ³ -A ³ -Z ² -A-,
A ¹ -A-, -A ⁴ -A- or -AA ⁴ -,

wherein XO or S and YH, C ₁ -C ₄ alkyl, F, Cl, Br, CN,
A ² , A ³ and A ⁴ each represent a 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl or a 1,3-dithiane-2,5-diyl group, each of which is in 1- or 4 Position can be substituted by C ₁ -C ₄ alkyl, F, Cl, Br, CF ₃ , CN, a piperidine-1,4-diyl or 1,4-bicyclo [2.2.2] octylene group, A or 1,4-phenylene group which is unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups, in which one or two CH groups can also be replaced by N,
Z ¹ and Z ² each -CO-O, -O-CO-, -CH ₂ CH ₂ -, -CHCN-CH ₂ -, -CH ₂ -CHCN-, -CH = CH-, -OCH ₂ -, - CH ₂ O-, -CH = N-, -N = CH-, -NO = N-, -N = NO- or a single bond and
R ³ alkyl with 1-15 C atoms, in which one or two non-adjacent CH ₂ groups by -O-, -CO-, -O-CO-, -CO-O-, and / or -CH = CH - can be replaced, denotes H, F, Cl, Br or CN,
as well as the acid addition salts of the basic among these compounds.

For the sake of simplicity, Cy in the following means a 1,4-cyclohexylene group, Oaz a 5,6-dihydro-4H-1,3-oxazine-2,5-diyl group, Taz a 5,6-dihydro-4H-1,3- thiazine-2,5-diyl group, Dio a 1,3-dioxane-2,5-diyl group, Dit a 1,3-dithiane-2,5-diyl group, Bi a bicyclo [2,2,2] octylene group, Pip a Piperidine-1,4-diyl group, Phe a 1,4-phenylene group, Pyr a pyrimidine-2,5-diyl group and Pyn a pyridazine-3,6-diyl group, where Phe and / or Pyr and / or Pyn are unsubstituted or by a or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups can be substituted.

The compounds of formula I can be used as components liquid crystalline phases are used, in particular  for displays based on the principle of twisted Cell, the guest-host effect, the effect of Deformation of erected phases or the effect of based on dynamic scattering.

It has now additionally been found that corresponding dihydroazines of the formula I in which one of the radicals R ¹ , R ² or R ^{3 is} NO ₂ or NCS and R ³ , A, A ¹ , A ² , A ³ , A ⁴ , Z ¹ and Z ^{2 have} the meaning given in the main application and are also particularly suitable as components of the liquid-crystalline phase. In particular, they have comparatively low viscosities and have no or only a slight tendency to form molecular associations. With their help, stable liquid-crystalline phases with a wide mesophase range and advantageous values for the optical and dielectric anisotropy can be obtained.

The compounds of the formula I are also distinguished through advantageous values for the ratio of elastic constants.

With the provision of the compounds of formula I will also generally the range of liquid crystalline Substances that can be found under various application technology Aspects for the production of liquid crystalline Mixtures are suitable, considerably widened.

The compounds of formula I have a wide range Scope of application. Depending on the selection of the Substituents can use these compounds as base materials serve from which liquid crystalline phases are composed for the most part; it can but also compounds of formula I liquid crystalline  Base materials from other classes of compounds added to, for example, the dielectric and / or optical anisotropy of such a dielectric to influence. The compounds of formula I are suitable themselves as intermediates for the manufacture of others Substances that are components of liquid crystalline Have dielectrics used.

The compounds of formula I are in a pure state colorless and form liquid crystalline mesophases in one conveniently located for electro-optical use Temperature range. Chemical, thermal and they are very stable against light.

The invention thus relates to the compounds corresponding to formula I of the main application, in which R ¹ and R ^{2 are} H, alkyl having 1-15 C atoms, in which also one or two non-adjacent CH ₂ groups are represented by -O-, -CO- , -O-CO-, -CO-O- and / or -CH = CH- may be replaced, R ^{3 is} -A ³ -Z ² , with the proviso that one of the radicals R ¹ , R ² or R ³ NO ₂ or NCS, and a process for the preparation of compounds of the formula I according to claim 1, characterized in that a compound which otherwise corresponds to the formula I but instead of H atoms is one or more reducible groups and / or Contains CC bonds, treated with a reducing agent,
or by cyclizing a carboxylic acid or thiocarboxamide with a 2-substituted 1,3-dihalopropane or a 2-substituted 3-halopropane amine,
or that a 2-substituted N-acyl-3-hydroxypropanamine is cyclized with base or phosphorus pentasulfide or a 2-substituted N-acyl-3-mercaptopropanamine is cyclized, or that for the preparation of esters of the formula I (in which Z ¹ and / or Z ² denotes -CO-O- or -O-CO- and / or R ¹ and / or R ² and / or R ³ contain a carboxyl group) a corresponding carboxylic acid or one of its reactive derivatives with a corresponding alcohol or one of its reactive derivatives or reacting an appropriate amine with thiophosgene,
or by converting an appropriate amine with carbon disulfide into a dithiocarbamate and treating it with hydrogen peroxide or a chlorocarbonic acid ester,
or by reacting a corresponding halide of the formula I, in which A ^{3 is} a cyclohexylene group, with a salt of thiocyanic acid,
or that for the preparation of ethers of the formula I (in which R ¹ and / or R ² and / or R ^{3 represents} an alkoxy group and / or Z ¹ and / or Z ^{2 is} a -OCH ₂ - or -CH ₂ O group) etherifying a corresponding hydroxy compound, and / or if appropriate converting a base of the formula I into one of its acid addition salts by treatment with an acid,
or that one optionally releases a compound of formula I from one of its acid addition salts by treatment with a base.

The invention furthermore relates to the use of the compounds of formula I as components of liquid crystalline Phases. The invention further relates to liquid crystalline phases containing at least a connection with the structural element 5,6-dihydro-4H-  1,3-oxazin-2,5-diyl or 5,6-dihydro-4H-1,3-thiazine-diyl, especially a compound of formula I, and liquid crystal Display elements that contain such phases. Such phases have particularly advantageous elastic ones Constants on.

Above and below, R ¹ , R ² , R ³ , A ¹ , A ² , A ³ , A ⁴ , A, Z ¹ and Z ^{2 have} the meaning given, unless expressly stated otherwise.

The compounds of formula I accordingly include Connections with two rings of sub-formulas Ia and Ib:

R ¹ -AZ ¹ -A ² -R ² (Ia)
R ¹ -AA ² -R ² (Ib)

Connections with three rings of the sub-formulas Ic to Il:

R ¹ -A ⁴ -AZ ¹ -A ² -R ² (Ic)
R ¹ -AA ⁴ -Z ¹ -A ² -R ² (Id)
R ¹ -AZ ¹ -A ² -Z ² -A ³ -R ³ (Ie)
R ³ -A ³ -Z ² -AZ ¹ -A ² -R ² (If)
R ¹ -AZ ¹ -A ² -A ³ -R ² (Ig)
R ¹ -AA ² -Z ² -A ³ -R ³ (Ih)
R ³ -A ³ -Z ² -AA ² -R ² (Ii)
R ³ -A ³ -AZ ¹ -A ² -R ² (Ij)
R ¹ -A ⁴ -AA ² -R ² (Ik)
R ¹ -AA ⁴ -A ² -R ² (Il),

Connections with four rings of the partial formulas Im to Iff:

R ³ -A ³ -Z ² -AZ ¹ -A ² -Z ² -A ³ -R ³ (Im)
R ³ -A ³ -AZ ¹ -A ² -A ³ -R ³ (In)
R ³ -A ³ -Z ² -AA ² -A ³ -R ³ (Io)
R ³ -A ³ -AA ² -Z ² -A ³ -R ³ (Ip)
R ¹ -A ⁴ -AZ ¹ -A ² -Z ² -A ³ -R ³ (Iq)
R ³ -A ³ -Z ² -A ⁴ -AZ ¹ -A ² -R ² (Ir)
R ¹ -AA ⁴ -Z ¹ -A ² -Z ² -A ³ -R ³ (Is)
R ³ -A ³ -Z ² -AA ⁴ -Z ¹ -A ² -R ² (It)
R ¹ -A ⁴ -AA ² -A ³ -R ³ (Iu)
R ¹ -AA ⁴ -A ² -A ³ -R ³ (Iv)
R ¹ -A ⁴ -AA ² -Z ² -A ³ -R ³ (Iw)
R ¹ -AA ⁴ -A ² -Z ² -A ³ -R ³ (Ix)
R ¹ -A ⁴ -AZ ¹ -A ² -A ³ -R ³ (Iy)
R ¹ -AA ⁴ -Z ¹ -A ² -A ³ -R ³ (Iz)
R ³ -A ³ -A ⁴ -AA ² -R ² (Iaa)
R ³ -A ³ -AA ⁴ -A ² -R ² (Ibb)
R ³ -A ³ -A ⁴ -AZ ¹ -A ² -R ² (Icc)
R ³ -A ³ -AA ⁴ -Z ¹ -A ² -R ² (Idd)
R ³ -A ³ -Z ² -A ⁴ -AA ² -R ² (Iee)
R ³ -A ³ -Z ² -AA ⁴ -A ² -R ² (Iff),

as well as connections with five rings of the sub-formulas Igg to Ill:

R ³ -A ³ -Z ² -A ⁴ -AZ ¹ -A ² -Z ² - A ³ -R ³ (Igg)
R ³ -A ³ -Z ² -AA ⁴ -Z ¹ -A ² -Z ² - A ³ -R ³ (Ihh)
R ³ -A ³ -A ⁴ -AA ² -A ³ -R ³ (Iii)
R ³ -A ³ -AA ⁴ -A ² -A ³ -R ³ (Ijj)
R ³ -A ³ -A ⁴ -AZ ¹ -A ² -A ³ -R ³ (Ikk)
R ³ -A ³ -AA ⁴ -Z ¹ -A ² -A ³ -R ³ (Ill).

In the compounds of the formulas above and below, one of the radicals R ¹ , R ² or R ³ preferably denotes NCS in addition to NO ₂ . R ¹ , R ² , R ^{3 also} mean alkyl or alkoxy.

A ² , A ³ and A ⁴ are preferred, Cy, Phe, Dio or Pyr, further preferably Oaz or Taz; the compound of the formula I preferably contains no more than one of the radicals Oaz, Taz, Dio, Dit, Pip, Bi, Pyn or Pyr.

Z ¹ and Z ² are preferably single bonds, in the second place preferably -CO-O-, -O-CO- or -CH ₂ CH ₂ groups.

If R ¹ and / or R ^{2 are} alkyl radicals and / or alkoxy radicals, they can be straight-chain or branched. They are preferably straight-chain, have 2, 3, 4, 5, 6 or 7 carbon atoms and accordingly preferably denote ethyl, propyl, butyl, pentyl, hexyl, heptyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy or heptoxy, furthermore methyl , Octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, methoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, tridecoxy or tetradecoxy.

Compounds of the formulas I with branched wing groups R ¹ or R ² or R ³ can occasionally be important because of their better solubility in the customary liquid-crystalline base materials, but in particular as chiral dopants if they are optically active.

Branched groups of this type usually contain no more than one chain branch. Preferred branched radicals R ¹ and R ² are isopropyl, 2-butyl (= 1-methylpropyl), isobutyl (= 2-methylpropyl), 2-methylbutyl, isopentyl (= 3-methylbutyl), 2-methylpentyl, 3-methylpentyl, 2 -Ethylhexyl, 2-propylpentyl, iospropoxy, 2-methylpropoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methylpentoxy, 3-methylpentoxy, 2-ethylhexoxy, 1-methylhexoxy, 1-methylheptoxy.

Formula I includes both the racemates of these compounds as well as the optical antipodes and their mixtures.

Among the compounds of the formulas I and Ia to Ill preferred are those in which at least one  of the residues contained therein one of the preferred Has meanings. Particularly preferred smaller ones Groups of compounds are those of the formulas I1 to I38:

R ¹ -Oaz-COO-Phe-R ² (I1)
R ¹ -Oaz-CH ₂ CH ₂ -Phe-R ² (I2)
R ¹ -Oaz-Phe-COO-Phe-R ² (I3)
R ¹ -Oaz-Phe-CH ₂ CH ₂ -Phe-R ² (I4)
R ¹ -Oaz-Phe-CH ₂ CH ₂ -Cy-R ² (I5)
R ¹ -Oaz-Phe-CH ₂ CH ₂ -Phe-Cy-R ³ (I6)
R ¹ -Oaz-Phe-CH ₂ CH ₂ -Phe-Dio-R ³ (I7)
R ¹ -Oaz-Phe-R ² (I8)
R ¹ -Oaz-Phe-Phe-R ² (I9)
R ¹ -Oaz-Phe-Phe-Cy-R ³ (I10)
R ¹ -Oaz-Phe-Phe-Dio-R ³ (I11)
R ¹ -Oaz-Cy-Phe-R ² (I12)
R ¹ -Cy-Oaz-Phe-R ² (I13)
R ¹ -Oaz-Cy-R ³ (I14)
R ¹ -Oaz-Cy-Cy-R ³ (I15)
R ¹ -Oaz-Pyr-R ² (I16)
R ¹ -Oaz-CH ₂ CH ₂ -Phe-Phe-R ² (I17)
R ¹ -Oaz-CH ₂ CH ₂ -Phe-Phe-Cy-R ³ (I18)
R ¹ -Oaz-CH ₂ CH ₂ -Phe-Cy-R ² (I19)
R ¹ -Taz-COO-Phe-R ² (I20)
R ¹ -Taz-CH ₂ CH ₂ -Phe-R ² (I21)
R ¹ -Taz-Phe-COO-Phe-R ² (I22)
R ¹ -Taz-Phe-CH ₂ CH ₂ -Phe-R ² (I23)
R ¹ -Taz-Phe-CH ₂ CH ₂ -Cy-R ² (I24)
R ¹ -Taz-Phe-CH ₂ CH ₂ -Phe-Cy-R ³ (I25)
R ¹ -Taz-CH ₂ CH ₂ -Phe-Dio-R ³ (I26)
R ¹ -Taz-Phe-R ² (I27)
R ¹ -Taz-Phe-Phe-R ² (I28)
R ¹ -Taz-Phe-Phe-Cy-R ³ (I29)
R ¹ -Taz-Phe-Phe-Dio-R ³ (I30)
R ¹ -Taz-Cy-Phe-R ² (I31)
R ¹ -Cy-Taz-Phe-R ² (I32)
R ¹ -Taz-Pyr-R ² (I33)
R ¹ -Taz-CH ₂ CH ₂ -Phe-Phe-R ² (I34)
R ¹ -Taz-CH ₂ CH ₂ -Phe-Phe-Cy-R ² (I35)
R ¹ -Taz-CH ₂ CH ₂ -Phe-Cy-R ² (I36)
R ¹ -Taz-Cy-R ³ (I37)
R ¹ -Taz-Cy-Cy-R ³ (I38)

In the compounds of formula I are those Stereoisomers preferred in which the rings are Cy, Dio, Dit and / or Pip are trans-1,4-disubstituted. Those of the above formulas, the one or several groups Oaz, Taz, Dio, Dit, Pip and / or Pyr contain, enclose the two possible 2,5- (Oaz, Taz, Dio, Dit, Pyr) or 1,4-position isomers (Pip).

Compounds of the formula I in which R ¹ , R ² and R ^{3 are} each straight-chain or at most single-branched alkyl groups or alkoxy groups having 1-10 C atoms and one of the radicals R ¹ , R ² or R ^{3 are} NCS or NO ₂ are particularly preferred.

The following smaller groups are particularly preferred of compounds in which -A- 5,6-dihydro-4H-1,3-thiazine 2,5-diyl or 5,6-dihydro-4H-1,3-oxazin-2,5-diyl, Phe 1,4- Phenylene, cyc 1,4-cyclohexylene, dio 1,3-dioxane-2,5-diyl and Pyr mean pyrimidine-2,5-diyl.

Alkyl preferably means straight-chain methyl, ethyl, Propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl or Decyl; Oxaalkyl preferably means straight-chain 2- Oxypropyl (= methoxymethyl), 2- (= ethoxymethyl) or  3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl, 2-, 3-, 4-, 5-, 6-, 7-, 8-, or 9-oxadecyl.

X means NCS or NO ₂

I. Methyl-A-Phe-X
Ethyl-A-Phe - X
Propyl-A-Phe-X
Butyl-A-Phe-X
Pentyl-A-Phe-X
Hexyl-A-Phe-X
Heptyl-A-Phe-X
Octyl-A-Phe-X
Nonyl-A-Phe-X
Decyl-A-Phe-X

II. Methoxy-A-Phe-X
Ethoxy-A-Phe-X
Propoxy-A-Phe-X
Butoxy-A-Phe-X
Pentoxy-A-Phe-X
Hexoxy-A-Phe-X
Heptoxy-A-Phe-X
Octoxy-A-Phe-X
Nonoxy-A-Phe-X
Decoxy-A-Phe-X
Alkyl-A- (3-F-Phe) -X

III.Methyl-A-Cyc-X
Ethyl-A-Cyc-X
Propyl-A-Cyc-X
Butyl-A-Cyc-X
Pentyl-A-Cyc-X
Hexyl-A-Cyc-X
Heptyl-A-Cyc-X
Octyl-A-Cyc-X
Nonyl-A-Cyc-X
Decyl-A-Cyc-X

IV.Methoxy-A-Cyc-X
Ethoxy-A-Cyc-X
Propoxy-A-Cyc-X
Butoxy-A-Cyc-X
Pentoxy-A-Cyc-X
Hexoxy-A-Cyc-X
Heptoxy-A-Cyc-X
Octoxy-A-Cyc-X
Nonoxy-A-Cyc-X
Decoxy-A-Cyc-X

V. Methoxycarbonyl-A-Cyc-X
Ethoxycarbonyl-A-Cyc-X
Propoxycarbonyl-A-Cyc-X
Butoxycarbonyl-A-Cyc-X
Pentoxycarbonyl-A-Cyc-X
Hexoxycarbonyl-A-Cyc-X
Heptoxycarbonyl-A-Cyc-X
Octoxycarbonyl-A-Cyc-X
Nonoxycarbonyl-A-Cyc-X
Decoxycarbonyl-A-Cyc-X

VI.Methylcarbonyloxy-A-Cyc-X
Ethylcarbonyloxy-A-Cyc-X
Propylcarbonyloxy-A-Cyc-X
Butylcarbonyloxy-A-Cyc-X
Pentylcarbonyloxy-A-Cyc-X
Hexylcarbonyloxy-A-Cyc-X
Heptylcarbonyloxy-A-Cyc-X
Octylcarbonyloxy-A-Cyc-X
Nonylcarbonyloxy-A-Cyc-X
Decylcarbonyloxy-A-Cyc-X

VII.Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X
Oxaalkyl-A-Cyc-X

VIII.Methyl-A-Phe-Phe-X
Ethyl-A-Phe-Phe-X
Propyl-A-Phe-Phe-X
Butyl-A-Phe-Phe-X
Pentyl-A-Phe-Phe-X
Hexyl-A-Phe-Phe-X
Heptyl-A-Phe-Phe-X
Octyl-A-Phe-Phe-X
Nonyl-A-Phe-Phe-X
Decyl-A-Phe-Phe-X
Alkyl-A-Phe- (3-F-Phe) -X

IX.Methoxy-A-Phe-Phe-X
Ethoxy-A-Phe-Phe-X
Propoxy-A-Phe-Phe-X
Butoxy-A-Phe-Phe-X
Pentoxy-A-Phe-Phe-X
Hexoxy-A-Phe-Phe-X
Heptoxy-A-Phe-Phe-X
Octoxy-A-Phe-Phe-X
Nonoxy-A-Phe-Phe-X
Decoxy-A-Phe-Phe-X

X. Methyl-Cyc-Phe-X
Ethyl-Cyc-Phe-X
Propyl-Cyc-Phe-X
Butyl-Cyc-Phe-X
Pentyl-Cyc-Phe-X
Hexyl-Cyc-Phe-X
Heptyl-Cyc-Phe-X
Octyl-Cyc-Phe-X
Nonyl-Cyc-Phe-X
Decyl-Cyc-Phe-X
Alkyl-A-Cyc- (3-F-Phe) -X

XI.Methoxy-A-Cyc-Phe-X
Ethoxy-A-Cyc-Phe-X
Propoxy-A-Cyc-Phe-X
Butoxy-A-Cyc-Phe-X
Pentoxy-A-Cyc-Phe-X
Hexoxy-A-Cyc-Phe-X
Heptoxy-A-Cyc-Phe-X
Octoxy-A-Cyc-Phe-X
Nonoxy-A-Cyc-Phe-X
Decoxy-A-Cyc-Phe-X

XII.Methyl-A-Cyc-Cyc-X
Ethyl-A-Cyc-Cyc-X
Propyl-A-Cyc-Cyc-X
Butyl-A-Cyc-Cyc-X
Pentyl-A-Cyc-Cyc-X
Hexyl-A-Cyc-Cyc-X
Heptyl-A-Cyc-Cyc-X
Octyl-A-Cyc-Cyc-X
Nonyl-A-Cyc-Cyc-X
Decyl-A-Cyc-Cyc-X

XIII.Methyl-Cyc-A-Phe-X
Ethyl-Cyc-A-Phe-X
Propyl-Cyc-A-Phe-X
Butyl-Cyc-A-Phe-X
Pentyl-Cyc-A-Phe-X
Hexyl-Cyc-A-Phe-X
Heptyl-Cyc-A-Phe-X
Octyl-Cyc-A-Phe-X
Nonyl-Cyc-A-Phe-X
Decyl-Cyc-A-Phe-X
Alkyl-Cyc-A- (3-F-Phe) -X

XIV.Methoxy-Cyc-A-Phe-X
Ethoxy-Cyc-A-Phe-X
Propoxy-Cyc-A-Phe-X
Butoxy-Cyc-A-Phe-X
Pentoxy-Cyc-A-Phe-X
Hexoxy-Cyc-A-Phe-X
Heptoxy-Cyc-A-Phe-X
Octoxy-Cyc-A-Phe-X
Nonoxy-Cyc-A-Phe-X
Decoxy-Cyc-A-Phe-X

XV.Methyl-Cyc-Phe-Phe-AX
Ethyl-Cyc-Phe-Phe-AX
Propyl-Cyc-Phe-Phe-AX
Butyl-Cyc-Phe-Phe-AX
Pentyl-Cyc-Phe-Phe-AX
Hexyl-Cyc-Phe-Phe-AX
Heptyl-Cyc-Phe-Phe-AX
Octyl-Cyc-Phe-Phe-AX
Nonyl-Cyc-Phe-Phe-AX
Decyl-Cyc-Phe-Phe-AX

XVI.Methyl-A-Pyr-X
Ethyl-A-Pyr-X
Propyl-A-Pyr-X
Butyl-A-Pyr-X
Pentyl-A-Pyr-X
Hexyl-A-Pyr-X
Heptyl-A-Pyr-X
Octyl-A-Pyr-X
Nonyl-A-Pyr-X
Decyl-A-Pyr-X

XVII.Alkyl-A-Pyr-Phe-X

XVIII.Methyl-A-COO-Phe-X
Ethyl-A-COO-Phe-X
Propyl-A-COO-Phe-X
Butyl-A-COO-Phe-X
Pentyl-A-COO-Phe-X
Hexyl-A-COO-Phe-X
Heptyl-A-COO-Phe-X
Octyl-A-COO-Phe-X
Nonyl-A-COO-Phe-X
Decyl-A-COO-Phe-X

XIX.Methoxy-A-COO-Phe-X
Ethoxy-A-COO-Phe-X
Propoxy-A-COO-Phe-X
Butoxy-A-COO-Phe-X
Pentoxy-A-COO-Phe-X
Hexoxy-A-COO-Phe-X
Heptoxy-A-COO-Phe-X
Octoxy-A-COO-Phe-X
Nonoxy-A-COO-Phe-X
Decoxy-A-COO-Phe-X

XX.Methyl-A-COO-Cyc-X
Ethyl-A-COO-Cyc-X
Propyl-A-COO-Cyc-X
Butyl-A-COO-Cyc-X
Pentyl-A-COO-Cyc-X
Hexyl-A-COO-Cyc-X
Heptyl-A-COO-Cyc-X
Octyl-A-COO-Cyc-X
Nonyl-A-COO-Cyc-X
Decyl-A-COO-Cyc-X

XXI.Methyl-A-COO-Phe-Phe-X
Ethyl-A-COO-Phe-Phe-X
Propyl-A-COO-Phe-Phe-X
Butyl-A-COO-Phe-Phe-X
Pentyl-A-COO-Phe-Phe-X
Hexyl-A-COO-Phe-Phe-X
Heptyl-A-COO-Phe-Phe-X
Octyl-A-COO-Phe-Phe-X
Nonyl-A-COO-Phe-Phe-X
Decyl-A-COO-Phe-Phe-X

XXII.Methyl-A-Phe-COO-Cyc-X
Ethyl-A-Phe-COO-Cyc-X
Propyl-A-Phe-COO-Cyc-X
Butyl-A-Phe-COO-Cyc-X
Pentyl-A-Phe-COO-Cyc-X
Hexyl-A-Phe-COO-Cyc-X
Heptyl-A-Phe-COO-Cyc-X
Octyl-A-Phe-COO-Cyc-X
Nonyl-A-Phe-COO-Cyc-X
Decyl-A-Phe-COO-Cyc-X

XXIII.Methyl-A-Phe-COO-Phe-X
Ethyl-A-Phe-COO-Phe-X
Propyl-A-Phe-COO-Phe-X
Butyl-A-Phe-COO-Phe-X
Pentyl-A-Phe-COO-Phe-X
Hexyl-A-Phe-COO-Phe-X
Heptyl-A-Phe-COO-Phe-X
Octyl-A-Phe-COO-Phe-X
Nonyl-A-Phe-COO-Phe-X
Decyl-A-Phe-COO-Phe-X

XXIV.Methoxy-A-Phe-COO-Phe-X
Ethoxy-A-Phe-COO-Phe-X
Propoxy-A-Phe-COO-Phe-X
Butoxy-A-Phe-COO-Phe-X
Pentoxy-A-Phe-COO-Phe-X
Hexoxy-A-Phe-COO-Phe-X
Heptoxy-A-Phe-COO-Phe-X
Octoxy-A-Phe-COO-Phe-X
Nonoxy-A-Phe-COO-Phe-X
Decoxy-A-Phe-COO-Phe-X

XXV. Alkyl-A-Phe-COO- (3-F-Phe) -X
Alkyl-A-Phe-CH ₂ CH ₂ - (3-F-Phe) -X
Alkyl-A-Phe-CH ₂ O- (3-F-Phe) -X

XXVI.Methyl-A-Cyc-COO-Cyc-X
Ethyl-A-Cyc-COO-Cyc-X
Propyl-A-Cyc-COO-Cyc-X
Butyl-A-Cyc-COO-Cyc-X
Pentyl-A-Cyc-COO-Cyc-X
Hexyl-A-Cyc-COO-Cyc-X
Heptyl-A-Cyc-COO-Cyc-X
Octyl-A-Cyc-COO-Cyc-X
Nonyl-A-Cyc-COO-Cyc-X
Decyl-A-Cyc-COO-Cyc-X

XXVII.Methyl-A-Cyc-COO-Phe-X
Ethyl-A-Cyc-COO-Phe-X
Propyl-A-Cyc-COO-Phe-X
Butyl-A-Cyc-COO-Phe-X
Pentyl-A-Cyc-COO-Phe-X
Hexyl-A-Cyc-COO-Phe-X
Heptyl-A-Cyc-COO-Phe-X
Octyl-A-Cyc-COO-Phe-X
Nonyl-A-Cyc-COO-Phe-X
Decyl-A-Cyc-COO-Phe-X

XXVIII.Methoxy-A-Cyc-COO-Phe-X
Ethoxy-A-Cyc-COO-Phe-X
Propoxy-A-Cyc-COO-Phe-X
Butoxy-A-Cyc-COO-Phe-X
Pentoxy-A-Cyc-COO-Phe-X
Hexoxy-A-Cyc-COO-Phe-X
Heptoxy-A-Cyc-COO-Phe-X
Octoxy-A-Cyc-COO-Phe-X
Nonoxy-A-Cyc-COO-Phe-X
Decoxy-A-Cyc-COO-Phe-X

XXIX.Methyl-A-OCO-Cyc-X
Ethyl-A-OCO-Cyc-X
Propyl-A-OCO-Cyc-X
Butyl-A-OCO-Cyc-X
Pentyl-A-OCO-Cyc-X
Hexyl-A-COO-Cyc-X
Heptyl-A-OCO-Cyc-X
Octyl-A-OCO-Cyc-X
Nonyl-A-OCO-Cyc-X
Decyl-A-OCO-Cyc-X

XXX.Methyl-A-OCO-Phe-X
Ethyl-A-OCO-Phe-X
Propyl-A-OCO-Phe-X
Butyl-A-OCO-Phe-X
Pentyl-A-OCO-Phe-X
Hexyl-A-OCO-Phe-X
Heptyl-A-OCO-Phe-X
Octyl-A-OCO-Phe-X
Nonyl-A-OCO-Phe-X
Decyl-A-OCO-Phe-X

XXXI.Methoxy-A-OCO-Phe-X
Ethoxy-A-OCO-Phe-X
Propoxy-A-OCO-Phe-X
Butoxy-A-OCO-Phe-X
Pentoxy-A-OCO-Phe-X
Hexoxy-A-OCO-Phe-X
Heptoxy-A-OCO-Phe-X
Octoxy-A-OCO-Phe-X
Nonoxy-A-OCO-Phe-X
Decoxy-A-OCO-Phe-X

XXXII.Methyl-A-OCO-Dio-X
Ethyl-A-OCO äDio-X
Propyl-A-OCO-Dio-X
Butyl-A-OCO-Dio-X
Pentyl-A-OCO-Dio-X
Hexyl-A-OCO-Dio-X
Heptyl-A-OCO-Dio-X
Octyl-A-OCO-Dio-X
Nonyl-A-OCO-Dio-X
Decyl-A-OCO-Dio-X

XXXXIII.Methyl-A-CH ₂ CH ₂ -Phe-Phe-X
Ethyl-A-CH ₂ CH ₂ -Phe-Phe-X
Propyl-A-CH ₂ CH ₂ -Phe-Phe-X
Butyl-A-CH ₂ CH ₂ -Phe-Phe-X
Pentyl-A-CH ₂ CH ₂ -Phe-Phe-X
Hexyl-A-CH ₂ CH ₂ -Phe-Phe-X
Heptyl-A-CH ₂ CH ₂ -Phe-Phe-X
Octyl-A-CH ₂ CH ₂ -Phe-Phe-X
Nonyl-A-CH ₂ CH ₂ -Phe-Phe-X
Decyl-A-CH ₂ CH ₂ -Phe-Phe-X

XXXIV.Methyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Ethyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Propyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Butyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Pentyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Hexyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Heptyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Octyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Nonyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Decyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X

XXXV. Methyl-A-CH ₂ CH ₂ -Phe- (3-F-Phe) -X
Ethyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Propyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Butyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Pentyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Hexyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Heptyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Octyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Nonyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X
Decyl-A-CH ₂ CH ₂ -Phe- (2-F-Phe) -X

XXXVI.Methyl-A-CH ₂ O-Phe-Pyr-X
Ethyl-A-CH ₂ O-Phe-Pyr-X
Propyl-A-CH ₂ O-Phe-Pyr-X
Butyl-A-CH ₂ O-Phe-Pyr-X
Pentyl-A-CH ₂ O-Phe-Pyr-X
Hexyl-A-CH ₂ O-Phe-Pyr-X
Heptyl-A-CH ₂ O-Phe-Pyr-X
Octyl-A-CH ₂ O-Phe-Pyr-X
Nonyl-A-CH ₂ O-Phe-Pyr-X
Decyl-A-CH ₂ O-Phe-Pyr-X

XXXVII.Methyl-A-CH ₂ CH ₂ -Cyc-X
Ethyl-A-CH ₂ CH ₂ -Cyc-X
Propyl-A-CH ₂ CH ₂ -Cyc-X
Butyl-A-CH ₂ CH ₂ -Cyc-X
Pentyl-A-CH ₂ CH ₂ -Cyc-X
Hexyl-A-CH ₂ CH ₂ -Cyc-X
Heptyl-A-CH ₂ CH ₂ -Cyc-X
Octyl-A-CH ₂ CH ₂ -Cyc-X
Nonyl-A-CH ₂ CH ₂ -Cyc-X
Decyl-A-CH ₂ CH ₂ -Cyc-X

The compounds of formula I are known per se Methods produced as described in the literature (e.g. in the standard works such as Houben-Weyl, methods of organic chemistry, Georg-Thieme-Verlag, Stuttgart) are described, namely under reaction conditions, known and suitable for the above-mentioned implementations are. You can also from well-known, here make use of variants not mentioned in more detail.

If desired, the starting materials can also be in situ are formed such that they can be removed from the reaction mixture not isolated, but immediately to the Reacts compounds of formula I.

The compounds of the formula I can be prepared in this way be by a connection that otherwise the Formula I corresponds, but instead of H atoms one or more reducible groups and / or C-C bonds contains, reduced.  

As reducible groups are preferably carbonyl groups, in particular keto groups, further z. B. free or esterified hydroxyl groups or aromatically bonded halogen atoms. Preferred starting materials for the reduction correspond to the formula I, but instead of a cyclohexane ring, a cyclohexene ring or cyclohexanone ring and / or instead of a -CH ₂ CH ₂ group, a -CH = CH group and / or instead of a -CH ₂ - Group contain a -CO group and / or instead of an H atom a free or a functional (e.g. in the form of its p-toluenesulfonate) modified OH group.

The reduction can e.g. B. done by catalytic hydrogenation at temperatures between 0 ° and about 200 ° and pressures between about 1 and 200 bar in an inert solvent, for. B. an alcohol such as methanol, ethanol or isopropanol, an ether such as tetrahydrofuran (THF) or dioxane, an ester such as ethyl acetate, a carboxylic acid such as acetic acid or a hydrocarbon such as cyclohexane. Suitable catalysts are suitably noble metals such as Pt or Pd, which can be used in the form of oxides (e.g. PtO ₂ , PdO), on a support (e.g. Pd on carbon, calcium carbonate or strontium carbonate) or in finely divided form .

Ketones can also by the methods of Clemmensen (with zinc, amalgamated zinc or tin and hydrochloric acid, suitably in aqueous-alcoholic solution or in a heterogeneous phase with water / toluene at temperatures between about 80 and 120 °) or Wolff-Kishner (with hydrazine, expediently reduced in the presence of alkali such as KOH or NaOH in a high-boiling solvent such as diethylene glycol or triethylene glycol at temperatures between about 100 and 200 °) to the corresponding compounds of the formula I which contain alkyl groups and / or -CH ₂ CH ₂ bridges .

Reductions with complex hydrides are also possible. For example, arylsulfonyloxy groups can be removed reductively with LiAlH ₄ , in particular p-toluenesulfonyloxymethyl groups can be reduced to methyl groups, expediently in an inert solvent such as diethyl ether or THF at temperatures between about 0 to 100 °. Double bonds can be hydrogenated (even in the presence of CN groups!) With NaBH ₄ or tributyltin hydride in methanol.

The compounds of the formula are particularly advantageous I by cyclization of carboxylic acid or thiocarboxamides with a 2-substituted 1,3-dihalopropane or a 2-substituted 3-halopropane amine receive. Cyclization of amides leads to dihydro-4H- 1,3-oxazines of the formula I, cyclization of thioamides leads to dihydro-4H-1,3-thiazines of the formula I.

The amides used as starting materials are according to known methods such. B. from carboxylic acids or their reactive derivatives by reaction with ammonia available, such as B. described in Houben-Weyl, methods of Organic Chemistry, Vol. VIII, Georg-Thieme-Verlag, Stuttgart. Examples of reactive carboxylic acid derivatives are Acid chlorides or anhydrides, esters or Find nitriles. Thioamides can e.g. B. from Nitriles with hydrogen sulfide can be obtained.

The production of some of the known raw materials 2,3-disubstituted propanamines used e.g. B. from 2-substituted 1,3-propanediols or from 2-substituted 3-aminopropanols, which in turn for example by reduction from the corresponding Carboxylic acids or their derivatives are accessible, and according to standard methods of organic chemistry the halogen compounds in question are implemented.  

The reactants are without solvent or expediently in the presence of an inert solvent cyclized together.

Alcohols are preferably suitable as inert solvents such as methanol, ethanol, isopropanol, n-butanol, Isoamyl alcohol, glycols and their ethers such as ethylene glycol, Diethylene glycol, ethylene glycol monomethyl or -monoethyl ether (methyl glycol or ethyl glycol), further Ethers such as tetrahydrofuran, dioxane or ethylene glycol dimethyl ether (Diglyme), as well as amides such as dimethylformamide, Hexamethylphosphoric triamide, dimethylacetamide or N-methylpyrrolidone, also sulfoxides such as dimethyl sulfoxide or sulfolane and hydrocarbons such as pentane, Hexane, cyclohexane, benzene or toluene. The reaction temperatures are usually between 0 ° C and the boiling point of the solvent, preferably between about 50 ° C and 150 ° C. The raw materials can without the addition of another reaction partner are implemented with each other, but is appropriate the presence of a base to remove the resulting Hydrogen halide. Suitable bases are e.g. B. alkali metal amides, alkali and alkaline earth metal hydroxides, carbonates and bicarbonates and ammonia, strong organic bases and basic ion exchangers. Preferred bases are alkali hydroxides and organic ones Bases, especially potassium and sodium hydroxide, pyridine and triethylamine.

In a further advantageous method, a 2- substituted N-acyl-3-hydroxypropanamine with base or Phosphorus pentasulfide cyclized or a 2-substituted N-acyl-3-mercaptopropanamine can be cyclized. The cyclization such amides can be among the same as for the implementation of the amides and thioamides with the halogen propanes described reaction conditions using the same bases and solvents.  

The N-acylpropanamines used as starting materials can z. B. according to the known methods for Production of carboxamides (such as in Houben- Weyl, Methods of Organic Chemistry, Vol. VIII, Georg- Thieme-Verlag, Stuttgart) from the corresponding Amines with carboxylic acids or their reactive Get descendants.

Esters of the formula I can also be esterified corresponding carboxylic acids (or their reactive Derivatives) with alcohols or phenols (or their reactive derivatives) will.

As reactive derivatives of the carboxylic acids mentioned the acid halides are particularly suitable the chlorides and bromides, furthermore the anhydrides, e.g. B. also mixed anhydrides, azides or esters, in particular Alkyl esters with 1-4 C atoms in the alkyl group.

As reactive derivatives of the alcohols mentioned or Phenols come in particular the corresponding metal alcoholates or phenolates, preferably an alkali metal like Na or K, into consideration.

The esterification is advantageous in the presence of a inert solvent performed. Are well suited in particular ethers such as diethyl ether, di-n-butyl ether, THF, dioxane or anisole, ketones such as acetone, butanone or cyclohexanone, amides such as DMF or phosphoric acid hexamethyltriamide, Hydrocarbons like benzene, Toluene or xylene, halogenated hydrocarbons such as carbon tetrachloride or tetrachlorethylene and sulfoxides such as dimethyl sulfoxide or sulfolane. Not with water Miscible solvents can be beneficial at the same time  for azeotropically distilling off during esterification formed water can be used. Occasionally can also an excess of an organic base, e.g. B. pyridine, Quinoline or triethylamine as a solvent for the Esterification can be applied. The esterification can also in the absence of a solvent, e.g. B. by simple Heating the components in the presence of sodium acetate, be performed. The reaction temperature is usually between -50 ° and + 250 °, preferably between -20 ° and + 80 °. Are at these temperatures the esterification reactions usually after 15 minutes ended up to 48 hours.

In particular, the reaction conditions depend on the Esterification largely depends on the nature of the used Starting materials. So is a free carboxylic acid a free alcohol or phenol usually in the presence a strong acid, for example one Mineral acid such as hydrochloric acid or sulfuric acid. A preferred mode of reaction is implementation an acid anhydride or, in particular, an acid chloride with an alcohol, preferably in one basic environment, with alkali metal hydroxides in particular as bases such as sodium or potassium hydroxide, alkali metal carbonates or hydrogen carbonates such as sodium carbonate, Sodium hydrogen carbonate, potassium carbonate or Potassium hydrogen carbonate, alkali metal acetates such as sodium or potassium acetate, alkaline earth metal hydroxides such as calcium hydroxide or organic bases such as triethylamine, pyridine, Lutidine, collidine or quinoline are important are. Another preferred embodiment of the Esterification consists in that the alcohol or the phenol first in the sodium or potassium alcoholate or -phenolate transferred, e.g. B. by treatment with ethanolic sodium or potassium hydroxide solution, this isolated  and together with sodium bicarbonate or Potassium carbonate with stirring in acetone or diethyl ether suspended and this suspension with a Solution of acid chloride or anhydride in diethyl ether, Acetone or DMF added, expediently at temperatures between about -25 ° and + 20 °.

The preparation of mustard oils of the formula I (in which R ¹ , R ² or R ^{3 is} NCS) is advantageously carried out by reacting corresponding amines with thiophosgene, as described, for example, in German patent specification 11 17 257.

Such amines of the formula I, in which R ¹ , R ² or R ^{3 represents} an amino group, are known or can be obtained by known methods. So nitro compounds or oximes z. B. with hydrogen under metal catalysis or by means of complex hydrides to amino compounds.

Aliphatic or aromatic halogen compounds, such as chlorides, bromides and iodides, with ammonia or an ammonia equivalent such as. B. Phthalimide potassium under metal salt catalysis, in particular with the addition of copper and / or its salts to amines be implemented.

The reduction partners are without solvents or expediently in the presence of an inert solvent reacted with each other.

Suitable diluents are preferably ethers such as Diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, Amides such as dimethylformamide, hexamethylphosphoric triamide, Hydrocarbons such as hexane, cyclohexane, benzene,  Toluene, xylene, halogenated hydrocarbons such as dichloromethane, Chloroform, carbon tetrachloride, tetrachlorethylene, Sulfoxides such as dimethyl sulfoxide, sulfolane and others organic solvents such as acetonitrile and nitromethane. Also water or mixtures of these solvents with water are suitable for the above implementation. The reaction temperatures are between -20 and + 100 °, preferably between 0 and 50 °. At these temperatures the implementations are usually after 30 minutes 24 hours ended.

In a further advantageous method, corresponding Halides of formula I with a salt of Reacts thiocyanic acid. Suitable salts for this are for example ammonium, sodium and potassium rhodanide. The reaction is advantageous in the presence of an inert performed non-polar solvent. Are well suited in particular hydrocarbons such as hexane, petroleum ether, Ligroin, cyclohexane, benzene, toluene and xylene. The reaction temperatures are between 0 and 150 °, preferably between 20 and 100 °. At these temperatures they are Reactions usually complete after 1 to 60 hours.

Finally, amines of the formula I in which R ¹ R ² or R ^{3 are} an amino group can also be converted with carbon disulfide into a dithiocarbamate and these can be further converted to mustard oils of the formula I under the influence of various reagents. Reagents suitable for carrying out this reaction sequence are, for example, hydrogen peroxide (cf. DE-21 05 473), cyanogen chloride (DE-26 03 508), cyanuric chloride (DE-19 35 302), chlorocarbonate (DE-11 78 423), alkali hypochlorite or alkali chlorite ( DE 9 52 083), phosgene (DE-10 68 250) and heavy metal salts (Dains et al., Org. Synth. Coll. Vol. 1 (1964) 447).

The preparation of the dithiocarbamates to that of the formula I. corresponding amino compounds and carbon disulfide expediently takes place in an inert solvent in the presence of an amine. Suitable solvents are for example hydrocarbons such as hexane, petroleum ether, Ligroin, cyclohexane, benzene, toluene and xylene. As an amine are preferably tertiary amines such as Pyridine, triethylamine or ethyldiisopropylamine are used. The ammonium dithiocarbamates obtained can by e.g. B. centrifugation or filtration, the However, they can also be used in situ to produce mustard oils of the formula I be implemented.

The reaction temperatures for the preparation of the dithiocarbamates are between -20 and + 100 °, preferably between 0 and 40 °. At these temperatures they are Reactions usually complete after 1 to 24 hours.

To convert the ammonium dithiocarbamates is preferred with chlorinated carbonic acid esters or hydrogen peroxide implemented.

The ammonium dithiocarbamates isolated or obtained in situ can be conveniently in the presence a suitable solvent such as ether such as diethyl ether, tetrahydrofuran, dioxane and halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane in the case of chlorocarbonic acid esters or water, formic acid, acetic acid react in the case of hydrogen peroxide. At reaction temperatures of -20 to 100 °, preferably between 0 and 80 °, the implementations are usually finished after 1 to 24 hours.  

Particularly suitable for the production of mustard oils Formula I is the reaction of suitable amines with carbon disulfide and triethylamine to triethylammonium dithiocarbamates and converting them into mustard oils by treatment with chlorinated carbonate or hydrogen peroxide.

Ethers of the formula I (in which R ¹ or R ² or R ^{3 is} an alkoxy group and / or in which Z ¹ and / or Z ^{2 is} a -OCH ₂ - or a -CH ₂ O group) by etherification of corresponding hydroxy compounds are preferred Corresponding phenols, available, the hydroxy compound expediently first in a corresponding metal derivative, for. B. is converted into the corresponding alkali metal alcoholate or alkali metal phenolate by treatment with NaH, NaNH ₂ , NaOH, KOH, Na ₂ CO ₃ or K ₂ CO ₃ . This can then be reacted with the corresponding alkyl halide, sulfonate or dialkyl sulfate, advantageously in an inert solvent such as acetone, 1,2-dimethoxyethane, DMF or dimethyl sulfoxide or even an excess of aqueous or aqueous-alcoholic NaOH or KOH at temperatures between about 20 ° and 100 °.

Compounds of the formula I in which R ¹ and / or R ² and / or R ^{3 are} F, Cl, Br or CN can also be obtained from the corresponding diazonium salts by exchanging the diazonium group for a fluorine, chlorine or bromine atom or for a CN Group, e.g. B. can be obtained by the methods of Schiemann or Sandmeyer.

The diazonium salts are e.g. B. producible by nitration of compounds corresponding to formula I, but instead of the radicals R ¹ and / or R ² and / or R ³ contain one (or two) hydrogen atom (s), reduction to the corresponding amines and diazotization, for example with NaNO ₂ or KNO ₂ in aqueous solution at temperatures between about -10 and + 10 °.

The diazonium group can be replaced by fluorine diazotize in anhydrous hydrofluoric acid and then heat, or you set with tetrafluoroboric acid to the diazonium tetrafluoroborates, which are then thermally decomposed.

An exchange for Cl, Br or CN is expediently achieved by reaction of the aqueous diazonium salt solution with Cu ₂ Cl ₂ , Cu ₂ Br ₂ or Cu ₂ (CN) ₂ using the Sandmeyer method.

A base of formula I can with an acid in the associated Acid addition salt can be transferred. For this Implementation, inorganic acids can be used e.g. B. sulfuric acid, nitric acid, hydrohalic acids such as hydrochloric acid or hydrobromic acid, Phosphoric acids such as orthophosphoric acid, sulfamic acid, also organic acids, especially aliphatic, alicyclic, araliphatic, aromatic or heterocyclic mono- or polybasic carbon, sulfone or sulfuric acids, e.g. B. formic acid, acetic acid, Propionic acid, pivalic acid, diethyl acetic acid, malonic acid, Succinic acid, pimelic acid, fumaric acid, maleic acid, Lactic acid, tartaric acid, malic acid, benzoic acid, Salicylic acid, 2- or 3-phenylpropionic acid, citric acid, Gluconic acid, ascorbic acid, nicotinic acid, isonicotinic acid, Methane or ethanesulfonic acid, ethanedisulfonic acid, 2-hydroxyethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, naphthalene mono- and disulfonic acids, Lauryl sulfuric acid.

Conversely, it is possible to use an acid addition salt a compound of formula I, the base of formula I. by treatment with a base, e.g. B. with a strong inorganic base such as KOH or NaOH.  

The liquid-crystalline phases according to the invention consist of 2 to 25, preferably 3 to 15 components, including at least one connection of the Formula I. The other ingredients are preferred selected from the nematic or nematogenic Substances, especially the known substances, from the classes of azoxybenzenes, benzylidene anilines, Biphenyls, terphenyls, phenyl or Cyclohexylbenzoate, cyclohexane-carboxylic acid phenyl or cyclohexyl esters, phenylcyclohexanes, cyclohexylbiphenyls, Cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-bis-cyclohexylbenzenes, 4,4'-bis- cyclohexylbiphenyls, phenyl- or cyclohexylpyrimidines, Phenyl or cyclohexyl dioxanes, phenyl or Cyclohexyldithiane, 1,2-bis-phenylethane, 1,2-bis cyclohexylethane, 1-phenyl-2-cyclohexylethane, optionally halogenated stilbene, benzylphenyl ether, Tolanes and substituted cinnamic acids.

The most important as components of such liquid crystalline Phases in question connections can be characterized by Formula II,

R′-L-G-E-R ″ (II)

where L and E each have a carbocyclic or heterocyclic ring system from that from 1,4-disubstituted benzene and Cyclohexane rings, 4,4′-disubstituted biphenyl, Phenylcyclohexane and cyclohexylcyclohexane systems, 2,5-disubstituted pyrimidine and 1,3-dioxane rings, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, Quinazoline and tetrahydroquinazoline formed Group,

G -CH = CH - N (O) = N- -CH = CY - CH = N (O) - -C≡C - CH ₂ -CH ₂ - -CO-O - CH ₂ -O- -CO-S - CH ₂ -S- -CH = N - COO-Phe-COO-

or a CC single bond, Y halogen, preferably chlorine, or -CN, and R ′ and R ″ alkyl, alkoxy, alkanoyloxy or alkoxycarbonyloxy having up to 18, preferably up to 8 carbon atoms, or one of these radicals also CN, NC, NO ₂ , CF ₃ , F, Cl or Br mean.

Most of these compounds are R ′ and R ″ different from one another, one of these residues mostly is an alkyl or alkoxy group. But others too Variants of the proposed substituents are common. Many such substances or mixtures thereof are commercially available. All of these substances are can be produced by methods known from the literature.

The liquid-crystalline phases according to the invention contain about 0.1 to 99, preferably 10 to 95%, one or several compounds of formula I. Also preferred are liquid crystalline phases that are 0.1-50, in particular 0.5-30% of one or more compounds of the Formula I included. Also isotropic compounds of the Formula I can be used in the phases according to the invention will.

The preparation of the liquid-crystalline according to the invention Phases take place in the usual way. Usually the components are dissolved into one another, expediently at elevated temperature.  

By means of suitable additives, the liquid crystalline Phases are modified according to the invention so that they are known in all types of Liquid crystal display elements are used can.

Such additives are known to the expert and in the Literature described in detail. For example, you can Conductive salts, preferably ethyl-dimethyl-dodecyl-ammonium 4-hexyloxybenzoate, tetrabutylammonium tetraphenylboranate or complex salts of crown ethers (cf. e.g. I. Haller et al., Mol. Cryst. Liq. Cryst. Volume 24, pages 249-258 (1973)) to improve conductivity, dichroic Dyes for the production of colored guest-host systems or substances for changing the dielectric Anisotropy, viscosity and / or orientation the nematic phases are added. Such Substances are e.g. B. in DE-OS 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430, 28 53 728 and 29 02 177.

The following examples are intended to illustrate the invention, without limiting it. F. = melting point, K. = clearing point. Above and below mean percentages Weight percent; all temperatures are in degrees Celsius specified. "Usual work-up" means: one gives Add water, extract with methylene chloride, separate off, the organic phase dries, evaporates and cleans the product by crystallization and / or chromatography.

example 1

1.8 g of 4-nitrothiobenzamide (obtainable from 4-nitrobenzamide by reaction with phosphorus pentasulfide) and 2.7 g of 2-n-pentyl-1,3-dibromopropane (obtainable by reacting the corresponding diol with 48 percent hydrobromic acid in the presence of concentrated Sulfuric acid) are heated together to 120 ° C. After 2 hours, the mixture is allowed to cool, mixed with dilute sodium hydroxide solution and extracted with ether. After evaporation of the solvent and crystallization from isopropanol, 2- (4-hexyloxyphenyl) -4H-5-pentyl-5,6-dihydro-1,3-thiazine is obtained as yellow crystals.
F .: 55 °, K .: 68 °.

Similarly, the groups I, II, VIII, IX, XIII and XIV designated compounds obtained.

Example 2

1.7 g of 4-nitrocyclohexane carboxamide (available from 4-nitrocyclohexane carboxylic acid with thionyl chloride about the acid chloride and its reaction with ammonia) and 2.8 g of 2-hexyl-1,3-dibromopropane (available from the corresponding diol as specified in Example 1) Heated to 120 ° for 4 hours. After cooling with Alkaline sodium hydroxide solution and extracted with ether. To Evaporation of the solvent and crystallization is obtained 2- (4-nitrocyclohexyl) -4H-5-hexyl-5,6-dihydro- 1,3-oxazine.

The groups in III-VII and X-XII get designated connections.  

Example 3

24.6 g of 2- (4-aminophenyl) -4H-5-pentyl-5,6-dihydro-1,3- oxazin (obtained from the corresponding nitro compound according to Example 1 by catalytic hydrogenation in ethyl acetate with the addition of 5% palladium / activated carbon catalyst) are with 10 g of carbon disulfide and 30 ml Triethylamine in 600 ml of toluene stirred at 0 ° for 24 hours. After that, the deposited crystal mass of the triethylammonium dithiocarbamate filtered and with toluene washed.

The intermediate product is suspended in a mixture 500 ml of chloroform and 50 ml of triethylamine - Then 25 g of chlorocarbonic acid ethyl ester are added dropwise admitted. To remove excess triethylamine washed with dilute hydrochloric acid and steamed Solvent under reduced pressure. After crystallization the residue is obtained 2- (4-isothiocyanatophenyl) - 4H-5-pentyl-5,6-dihydro-1,3-oxazine.

Example 4

36.6 g of 2- (4'-aminobiphenyl-4-yl) -4H-5-heptyl-5,6-dihydro- 1,3-thiazine (made from 4-iodobenzoate thioamide and 2-heptyl-1,3-dibromopropane according to Example 1 of the main application to 2- (4-iodophenyl) -4H-5-heptyl-5,6-dihydro-1,3- thiazine, its coupling according to Ullmann with 4-bromonitrobenzene with copper addition and subsequent reduction as in Example 3) are described with 12 g of thiophosgene and 25 ml triethylamine in 300 ml chloroform for 24 hours at 0 ° touched.

The dithiocarbomat obtained by filtration becomes in portions in 150 ml of 30% hydrogen peroxide solution entered and then stirred for 2 hours at 40 °.  

It is allowed to cool and the product which has separated out is filtered off with suction. After crystallization from ethyl acetate, one obtains 2- (4-isothiocycanatobiphenyl-4'-yl) -4H-5-heptyl-5,6- dihydro-1,3-thiazine. Analogously, those in groups VIII and IX designated compounds obtained.

Example A

A mixture is made up:

26.5% 2- (4-isothiocyanatophenyl) -4H-5-heptyl-5,6- dihydro-1,3-thiazine 23% 2- (4-isothiocyanatophenyl) -4H-5-pentyl-5,6- dihydro-1,3-oxazine 18% 4-propyloxybenzoic acid (4-pentylphenyl) ester 13% 4- (4-pentylcyclohexyl) benzoic acid (4-propyl) phenyl) ester 11.5% 4- (4-butylcyclohexyl) benzoic acid (4-fluorophenyl) - ester 8% 1- (4- (4-butylcyclohexyl) cyclohexyl) -2- (4-hexyl- cyclohexyl) ethane

Example B

A mixture is made up:

33% 2- (4-nitrophenyl) -4H-5-pentyl-5,6-dihydro-1,3- thiazine 27% 2- (4-cyanophenyl) -5-hexylpyrimidine 17% 4- (4-propyloxycyclohexyl) pentylcyclohexane 13% 1-cyano-4-pentyl-cyclohexane-1-carboxylic acid- (4-propyl- cyclohexyl) ester 10% 4-propylcclohexane carboxylic acid- (2,3-dicyano-4-pentyl- phenyl) ester

Claims (7)

1. 5,6-dihydroazine derivatives of the formula I R ¹ -A ¹ -Z ¹ -A ² -R ² , 6 (I) in which
R ¹ and R ² H, alkyl with 1-15 C atoms, in which also one or two non-adjacent CH ₂ groups by -O-, -CO-, -O-CO-, -CO-O- and / or -CH = CH- can be replaced, R ³ -A ³ -Z ² ,
A ¹ -A-, -A ⁴ -A-, -AA ⁴ -, wherein XO or S and YH, C ₁ -C ₄ alkyl, F, Cl, Br, CN,
A ² , A ³ and A ⁴ each represent a 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, or a 1,3-dithiane-2,5-diyl group, each in 1- or 4-position can be substituted by C ₁ -C ₄ alkyl, F, Cl, Br, CF ₃ , CN, a piperidine-1,4-diyl or 1,4-bicyclo [2.2.2] octylene group, A or an 1,4-phenylene group which is unsubstituted or substituted by one or two F and / or Cl atoms and / or CH ₃ groups and / or CN groups, in which one or two CH groups can also be replaced by N,
Z ¹ and Z ² each -CO-O-, -O-CO-, -CH ₂ CH ₂ -, -CHCN-CH ₂ -, -CH ₂ -CHCN-, -CH = CH-, -OCH ₂ -, -CH ₂ O-, -CH = N-, -N = CH-, -NO = N-, -N = NO- or a single bond and
R ³ alkyl with 1-15 C atoms, in which one or two non-adjacent CH ₂ groups by -O-, -CO-, -O-CO-, -CO-O-, and / or -CH = CH - can be replaced means
and the acid addition salts of the basic among these compounds with the proviso that one of the radicals R ¹ , R ² or R ^{3 is} NO ₂ or NCS. 2. A process for the preparation of dihydroazines of the formula I according to claim 1, characterized in that a compound which otherwise corresponds to the formula I but contains one or more reducible groups and / or CC bonds instead of H atoms treated with a reducing agent,
or by cyclizing a carboxylic acid or thiocarboxamide with a 2-substituted 1,3-dihalopropane or a 2-substituted 3-halopropane amine,
or that a 2-substituted N-acyl-3-hydroxypropanamine is cyclized with base or phosphorus pentasulfide or a 2-substituted N-acyl-3-mercapto-propanamine is cyclized,
or that for the preparation of esters of the formula I (in which Z ¹ and / or Z ^{2 are} -CO-O- or -O-CO- and / or R ¹ and / or R ² and / or R ³ contain a carboxyl group) reacting a corresponding carboxylic acid or one of its reactive derivatives with a corresponding alcohol or one of its reactive derivatives,
or that for the preparation of ethers of the formula I (in which R ¹ and / or R ² and / or R ^{3 is} an alkoxy group and / or Z ¹ and / or Z ^{2 is} OCH ₂ or -CH ₂ O groups) is one etherified corresponding hydroxy compound,
or that a corresponding amine is treated with thiophosgene,
or by converting an appropriate amine with carbon disulfide into a dithiocarbamate and treating it with hydrogen peroxide or a chlorocarbonic acid ester,
or by reacting a corresponding halide of the formula I, in which A ^{3 is} a cyclohexylene group, with a salt of thiocyanic acid,
and / or if appropriate converting a base of the formula I into one of its acid addition salts by treatment with an acid,
or that one optionally releases a compound of formula I from one of its acid addition salts by treatment with a base. 3. Use of the compounds of formula I according to claim 1 as components of liquid crystalline phases. 4. Liquid crystalline phase with at least two liquid crystalline phases Components, characterized in that at least one component connects to the structural element 5,6-dihydro-4H-1,3-oxazin-2,5- is diyl or 5,6-dihydro-4H-1,3-thiazine-2,5-diyl.   5. Liquid crystalline phase according to claim 4 with at least two liquid crystalline components, thereby characterized in that at least one component is a compound of formula I according to claim 1. 6. Liquid crystal display element, characterized in that after a liquid crystalline phase Claim 4 contains. 7. Electro-optical display element according to claim 6, characterized in that it is a dielectric contains liquid crystalline phase according to claim 4.