Tetrahydrocarbazoles, a process for the preparation of those compounds, and the use thereof

Abstract

There are described tetrahydrocarbazoles of formula (1) or (2). The compounds are suitable as antimicrobial active ingredients.

Description

[0001] The present invention relates to novel tetrahydrocarbazoles, to a process for the preparation of those compounds and to the use thereof as antimicrobial active ingredients.

[0002] The tetrahydrocarbazoles according to the invention correspond to formula 1

[0003] wherein

[0004] R1 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20-alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkylcarbonyl, C1-C7alkoxycarbonyl, C3-C12cycloalkylcarbonyl, C3-C12-cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro,

[0005] R2 is hydrogen; hydroxy; C1-C20alkyl; C3-C12cycloalkyl; C1-C20hydroxyalkyl; C1-C20-hydroxyalkoxy; C1-C20aminoalkyl; N—C1-C20monoalkylamino-C1-C20alkyl; N—C1-C20-monoalkylaminohydroxy-C1-C20alkoxy; N,N—C1-C20dialkylamino-C1-C20alkyl; N,N—C1-C20dialkylaminohydroxy-C1-C20alkoxy; carboxy; carboxy-C1-C20alkyl ester, C1-C20-haloalkyl; C1-C20haloalkoxy; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12-cycloalkynyl; C1-C20alkoxy; C2-C20alkenyloxy; C2-C20alkynyloxy; halogen; cyano; C1-C7alkylcarbonyl; nitro; trifluoromethyl; or pentafluoroethyl;

[0006] R3 and R4 are each independently of the other hydrogen; or C1-C20alkyl; or R3 and R4 together denote a C2-C20alkylene radical; a C2-C20alkenylene radical; a C4-C20-alkynylene radical; or a C3-C20alkylene radical interrupted by —N(R6)—, it being possible for such bivalent radicals to be further substituted by one or more C1-C20alkyl, C3-C12-cycloalkyl, C2-C20alkenyl, C4-C12cycloalkenyl, C3-C20alkynyl, C4-C12cycloalkynyl, C1-C7alkoxycarbonyl, or phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro; or R3 and R4 together denote a bicyclo[x.y.z.]C4-C20alkylene; or bicyclo[x.y.z.]C4-C20alkylene interrupted by —N(R6)—, wherein x, y and z are each independently of the others from 0 to 10;

[0007] R5 is hydrogen; hydroxy; C1-C20alkyl; C1-C20alkoxy; C3-C12cycloalkyl; C2-C20alkenyl C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12-cyclolkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, triluoroethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0008] R6 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20-alkynyl; C4-C12cycloalkynyl; C1-C7alkoxycarbonyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12-cyclolkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0009] Q is —SO2—; —O—; or —(CO)—;

[0010] X is —CH—; or —N—;

[0011] m is from 1 to 3; and

[0012] t is 0 or 1.

[0013] C1-C20Alkyl denotes straight-chain or branched alkyl radicals, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl or tert-amyl, heptyl, octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl or eicosyl.

[0014] C3-C12Cycloalkyl is, for example, cyclopropyl, cyclobutyl, cyclopentyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclodocecyl and especially cyclohexyl.

[0015] Within the scope of the meanings given, alkenyl includes inter alia allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4dienyl, 3-methylbut-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, isododecenyl, n-dodec-2-enyl or n-octadec-4-enyl.

[0016] C1-C20Alkoxy denotes straight-chain or branched radicals, such as methoxy, ethoxy, propoxy, butoxy or pentyloxy, hexyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy or eicosyloxy.

[0017] Halogen is fluorine, chlorine, bromine or iodine.

[0018] Preference is given to the use of compounds of formula (1) or (2) wherein

[0019] R1 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkylcarbonyl, C1-C7alkoxycarbonyl, C3-C12cycloalkylcarbonyl, C3-C12-cycloalkoxyarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylmino or by nitro,

[0020] R2 is hydrogen; hydroxy; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; C1-C20alkoxy; C2-C20alkenyloxy; C2-C20alkynyloxy; halo cyano; C1-C7alkylcarbonyl; nitro; trifluoromethyl; or pentafluoroethyl;

[0021] R3 and R4 are each independently of the other hydrogen; or C1-C20alkyl; or R3 and R4 denote a C2-C20alkylene radical; a C2-C20alkenylene radical; a C4-C20alkynylene radical; or a C3-C20alkylene radical interrupted by —N(R6)—, it being possible for such bivalent radicals to be further substituted by one or more C1-C20alkyl, C3-C12cycloalkyl, C2-C20-alkenyl, C4-C12cycloalkenyl, C3-C20alkynyl, C4-C12cycloalkynyl, C1-C7alkoxycarbonyl, or phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12-cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0022] R5 is hydrogen; hydroxy; C1-C20alkyl; C1-C20alkoxy; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12-cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0023] R6 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; alkynyl; C4-C12cycloalkynyl; C1-C7alkoxycarbonyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12-cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluorom thyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0024] Q is —SO2—; —O—; or —(CO)—;

[0025] X is —CH—; or —N—;

[0026] m is from 1 to 3; and

[0027] t is 0 or 1.

[0028] In formula (1)

[0029] R1 is preferably hydrogen; C1-C20alkyl; phenyl or phenyl-C1-C5alkyl, and is especially hydrogen; or C1-C5alkyl.

[0030] Preference is given also to compounds of formula (1) wherein

[0031] R2 is hydrogen; C1-C20alkyl; C1-C20alkoxy; or halogen and is especially hydrogen; C1-C5alkyl; C1-C5alkoxy; or halogen.

[0032] Very special preference is given to compounds of formula 2

[0033] wherein

[0034] R1 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20-alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkylcarbonyl, C1-C7alkoxycarbonyl, C3-C12cycloalkylcarbonyl, C3-C12-cycloalkoxyarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylmino or by nitro,

[0035] R2 is hydrogen; hydroxy; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; C1-C20alkoxy; C2-C20alkenyloxy; C2-C20alkynyloxy; halogen; cyano; C1-C7alkylcarbonyl; nitro; trifluoromethyl; or pentafluoroethyl;

[0036] R5 is hydrogen; hydroxy; C1-C20alkyl; C1-C20alkoxy; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12-cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0037] R6 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkeny alkynyl; C4-C12cycloalkynyl; C1-C7alkoxycarbonyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C7alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12-cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0038] Q is —SO2—; —O—; or —(CO)—;

[0039] T1 is C2-C20calkylene; C2-C20alkenylene; C4-C20alkynylene; or C3-C20alkylene interrupted by 3

[0040] X is —CH—; or —N—;

[0041] s is from 1 to 4; and

[0042] t is 0 or 1.

[0043] Preference is given to compounds of formula (3) or (4) wherein

[0044] T1 is a —(CH2)2-12— radical and

[0045] R6 is hydrogen; or C1-C5alkyl,

[0046] and especially to compounds of formula (3) or (4) wherein

[0047] T1 is a —(CH2)3—, —(CH2)4—, —(CH2)5—, or —(CH2)10— radical; and

[0048] R6 is hydrogen; or C1-C5alkyl.

[0049] R5 in formula (1) is preferably hydrogen; C1-C20alkyl; phenyl or phenyl-C1-C5alkyl; and more especially hydrogen; C1-C5alkyl; or phenyl.

[0050] More especially preferred compounds according to the invention correspond to formula 4

[0051] wherein

[0052] R6′ and R6″ are each independently of the other hydrogen; C1-C20alkyl; C1-C7alkoxy-carbonyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C1-C7alkoxycarbonyl, N,N-mono- or di-C1-C20alkylamino or by nitro;

[0053] T1 is 5

[0054]  and

[0055] R1, R2, R5, R6 and X are as defined for formula (3).

[0056] In formulae (5) and (6) preferably

[0057] R6′, R6″ and R6 are each independently of the others hydrogen; C1-C20alkyl; C1-C7-alkoxycarbonyl; phenyl; or phenyl-C1-C5alkyl.

[0058] Special preference is given to compounds of formula (5) and (6) wherein R6′ and R6″ and R6 are each independently of the others hydrogen; C1-C5alkyl; C1-C7 alkoxycarbonyl; phenyl or benzyl.

[0059] Further preferred compounds according to the invention correspond to formula 6

[0060] wherein

[0061] R1 is hydrogen; or C1-C5alkyl;

[0062] R2 is hydrogen; C1-C4alkyl; Cl or Br,

[0063] R5 is hydrogen; C1-C5alkyl; or phenyl

[0064] R6′ and R6″ are each independently of the other hydrogen, C1-C5alkyl; or C1-C7alkoxy-carbonyl;

[0065] R6 is hydrogen; C1-C5alkyl; C1-C7alkylcarbonyl; or phenyl-C1-C5alkyl;

[0066] T1 is 7

[0067]  and

[0068] X is —CH—.

[0069] Compounds according to the invention are listed in Tables 1 a and b below by way of example:

TABLE 1a
General structural formula
	8	9
Compound of formula	R1	R2	10	R5	Yield [surfaces %]
9	H	H	—(CH2)4—	Ph	92
10	H	7-Br	—(CH2)4—	Ph	75
11	Me	H	—(CH2)4—	Ph	68
12	H	H	—(CH2)3—	Ph	93
13	H	H	11	Ph	67
14	H	H	—(CH2)5—	Ph	92
15	H	H	12	Ph	79
16	H	H	—(CH2)4—	H	48
17	H	H	—(CH2)4—	Et	55
18	H	7-Br	—(CH2)3—	Ph	96
19	H	7-Br	13	Ph	83
20	H	7-Br	—(CH2)5—	Ph	68
21	Me	H	—(CH2)3—	Ph	95
22	Me	H	14	Ph	64
23	Me	H	—(CH2)5—	Ph	75
24	Me	H	15	Ph	38
25	H	H	—(CH2)3—	H	86
26	H	H	16	H	95
27	H	H	—(CH2)5—	H	68
28	H	H	17	H	88
29	H	7-Br	—(CH2)4—	H	92
30	H	7-Br	—(CH2)3—	H	90
31	H	7-Br	18	H	41
32	H	7-Br	—(CH2)5—	H	79
33	H	7-Br	19	H	44
34	Me	H	—(CH2)4—	H	77
35	Me	H	—(CH2)3—	H	95
36	Me	H	20	H	84
37	Me	H	—(CH2)5—	H	87
38	H	H	—(CH2)3—	Et	91
39	H	H	21	Et	66
40	H	H	—(CH2)5—	Et	89
41	H	H	22	Et	57
42	H	7-Br	—(CH2)4—	Et	85
43	H	7-Br	—(CH2)3—	Et	90
44	H	7-Br	23	Et	47
45	H	7-Br	—(CH2)5—	Et	51
46	H	7-Br	24	Et	91
47	Me	H	—(CH2)4—	Et	94
48	Me	H	—(CH2)3—	Et	95
49	Me	H	25	Et	80
50	Me	H	—(CH2)5—	Et	90
51	H	9-Et	—(CH2)4—	Ph	95
52	H	H	26	Ph	96
53	H	H	isopropyl	Ph	59
54	H	H	27	H	19
55	H	H	28	H	85
56	H	H	29	H	44
57	H	H	30	H	65
58	H	H	31	H	62
59	H	H	32	H	49
60	H	H	33	H	37
61	H	H	—(CH2)10—	H	90
62	H	H	—(CH2)6—	H	63
63	H	H	34	H	81
64	H	H	isopropyl	H	28
65	H	H	Me	H	62
66	H	H	Et	H	58
67	H	H	35	H	58
68	H	7-Br	36	H	93
69	H	7-Br	37	H	93
70	H	7-Br	38	H	90
71	H	7-Br	39	H	93
72	H	7-Br	40	H	94
73	H	7-Br	—(CH2)6—	H	33
74	H	9-Et	—(CH2)4—	H	68
75	H	9-Et	—(CH2)3—	H	91
76	H	9-Et	41	H	99
77	H	9-Et	—(CH2)5—	H	93
78	H	9-Et	42	H	82
79	H	9-Et	43	H	56
80	H	9-Et	44	H	78
81	H	9-Et	45	H	36
82	H	9-Et	46	H	63
83	H	9-Et	47	H	74
84	H	9-Et	48	H	91
85	H	9-Et	49	H	64
86	H	9-Et	50	H	39
87	H	9-Et	51	H	26
88	H	9-Et	—(CH2)10—	H	64
89	H	9-Et	—(CH2)6—	H	86
90	H	9-Et	52	H	63
91	H	7-MeO	—(CH2)4—	H	93
92	H	7-MeO	—(CH2)3—	H	93
93	H	7-MeO	53	H	56
94	H	7-MeO	—(CH2)5—	H	71
95	H	7-MeO	54	H	10
96	H	7-MeO	55	H	88
97	H	7-MeO	56	H	22
98	H	7-MeO	57	H	76
99	H	7-MeO	58	H	60
100	H	7-MeO	59	H	83
101	H	7-MeO	60	H	94
102	H	7-MeO	61	H	79
103	H	7-MeO	62	H	74
104	H	7-MeO	63	H	84
105	H	7-MeO	64	H	80
106	H	7-MeO	—(CH2)10—	H	93
107	H	7-MeO	—(CH2)6—	H	34
108	H	7-MeO	65	H	27
109	H	H	—(CH2)4—	Me	54
110	H	H	—(CH2)3—	Me	81
111	H	H	66	Me	98
112	H	H	—(CH2)5—	Me	93
113	H	H	67	Me	47
114	H	H	68	Me	86
115	H	H	69	Me	16
116	H	H	70	Me	64
117	H	H	71	Me	98
118	H	H	72	Me	87
119	H	H	73	Me	98
120	H	H	74	Me	98
121	H	H	75	Me	83
122	H	H	76	Me	93
123	H	H	77	Me	89
124	H	H	—(CH2)10—	Me	95
125	H	H	—(CH2)6—	Me	43
126	H	H	78	Me	98
127	H	7-Br	—(CH2)4—	Me	92
128	H	7-Br	—(CH2)3—	Me	94
129	H	7-Br	79	Me	99
130	H	7-Br	—(CH2)5—	Me	76
131	H	7-Br	80	Me	69
132	H	7-Br	81	Me	97
133	H	7-Br	82	Me	22
134	H	7-Br	83	Me	92
135	H	7-Br	84	Me	95
136	H	7-Br	85	Me	69
137	H	7-Br	86	Me	84
138	H	7-Br	87	Me	75
139	H	7-Br	88	Me	87
140	H	7-Br	89	Me	16
141	H	7-Br	90	Me	73
142	H	7-Br	—(CH2)10—	Me	81
143	H	7-Br	—(CH2)6—	Me	97
144	H	7-Br	91	Me	92
145	H	9-Et	—(CH2)4—	Me	97
146	H	9-Et	—(CH2)3—	Me	97
147	H	9-Et	92	Me	46
148	H	9-Et	—(CH2)5—	Me	88
149	H	9-Et	93	Me	5
150	H	9-Et	94	Me	32
151	H	9-Et	95	Me	31
152	H	9-Et	96	Me	85
153	H	9-Et	97	Me	87
154	H	9-Et	98	Me	92
155	H	9-Et	99	Me	93
156	H	9-Et		Me	27
157	H	9-Et	100	Me	73
158	H	9-Et	101	Me	79
159	H	9-Et	102	Me	13
160	H	9-Et	103	Me	81
161	H	9-Et	—(CH2)10—	Me	98
162	H	9-Et	—(CH2)6—	Me	97
163	H	9-Et	104	Me	55
164	H	7-MeO	—(CH2)4—	Me	58
165	H	7-MeO	—(CH2)3—	Me	54
166	H	7-MeO	105	Me	93
167	H	7-MeO	—(CH2)5—	Me	96
168	H	7-MeO	106	Me	7
169	H	7-MeO	107	Me	82
170	H	7-MeO	108	Me	36
171	H	7-MeO	109	Me	71
172	H	7-MeO	110	Me	29
173	H	7-MeO	111	Me	80
174	H	7-MeO	112	Me	68
175	H	7-MeO	113	Me	95
176	H	7-MeO	114	Me	79
177	H	7-MeO	115	Me	89
178	H	7-MeO	116	Me	72
179	H	7-MeO	—(CH2)10—	Me	73
180	H	7-MeO	—(CH2)6—	Me	27
181	H	7-MeO	117	Me	95

[0070]

TABLE 1b
General structural formula
	118	119
Compound of formula	R1	R2	R2′	120	R4	Yield [surfaces %]
182	—H	—H	—H	121	—H	89
183	—H	—H	—H	122	—H	56
184	—H	—H	—H	123	—H	95
185	—H	—H	—H	—(CH2)13—	—H	82
186	—H	6-Me	—H	124	—H	93
187	—H	6-OMe	—H	—(CH2)5—	—H	90
188	—H	6-OMe	—H	—(CH2)10—	—H	50
189	—H	125	—H	—(CH2)5—	—H	85
190	—H	126	—H	127	—H	40
191	—H	7-F	—H	—(CH2)5—	—H	88
192	—H	7-F	—H	—(CH2)10—	—H	93
193	—H	7-F	—H	128	—H	94
194	—H	7-Me	—H	—(CH2)5—	—H	81
195	—H	7-Me	—H	—(CH2)10—	—H	96
196	—H	8-Cl	—H	—(CH2)6—	—H	87
197	—H	8-Cl	—H	—(CH2)10—	—H	44
198	—H	8-Cl	—H	—(CH2)2—	—H	97
199	—H	8-Cl	—H	129	—H	99
200	—H	6-COOMe	—H	—(CH2)2—	—H	66
201	—H	6-COOMe	—H	130	—H	82
202	—H	8-Me	—H	—(CH2)5—	—H	76
203	—H	8-Me	—H	131	—H	82
204	—H	8-F	—H	—(CH2)5—	—H	76
205	—H	8-F	—H	—(CH2)10—	—H	56
206	—H	8-F	—H	—(CH2)2—	—H	75
207	—H	8-F	—H	132	—H	90
208	—H	9-F	—H	—(CH2)5—	—H	93
209	—H	9-F	—H	—(CH2)10—	—H	30
210	—H	9-F	—H	—(CH2)2—	—H	89
211	—H	9-F	—H	133	—H	99
212	—H	8-CF3	—H	—(CH2)5—	—H	42
213	—H	8-CF3	—H	—(CH2)10—	—H	40
214	—H	8-CF3	—H	—(CH2)2—	—H	61
215	—H	8-CF3	—H	134	—H	71
216	—H	7-F	8-F	—(CH2)5—	—H	68
217	—H	7-F	8-F	—(CH2)10—	—H	90
218	—H	7-F	8-F	—(CH2)2—	—H	87
219	—H	7-F	8-F	135	—H	98
220	—H	9-Me	—H	—(CH2)5—	—H	95
221	—H	9-Me	—H	—(CH2)10—	—H	97
222	—H	9-Me	—H	136	—H	75
223	—H	6-Cl	—H	—(CH2)2—	—H	95
224	—H	6-Cl	—H	137	—H	91
225	—H	6-F	—H	—(CH2)2—	—H	94
226	—H	6-F	—H	138	—H	97
227	—H	9-OMe	—H	—(CH2)5—	—H	93
228	—H	9-OMe	—H	—(CH2)10—	—H	90
229	—H	9-OMe	—H	139	—H	98
230	—H	8-OMe	—H	—(CH2)5—	—H	84
231	—H	8-OMe	—H	140	—H	96
232	—H	7-COOMe	—H	—(CH2)5—	—H	87
233	—H	7-COOMe	—H	—(CH2)10—	—H	83
234	—H	7-COOMe	—H	—(CH2)2—	—H	54
235	—H	7-COOMe	—H	141	—H	57
236	—H	7-OMe	8-OMe	—(CH2)5—	—H	99
237	—H	7-OMe	8-OMe	—(CH2)10—	—H	69
238	—H	7-OMe	8-OMe	142	—H	58

[0071] The preparation of the tetrahydrocarbazoles according to the invention is carried out according to widely known methods in a 3-component reaction, as described in the publication by W. Noland et al., J. Heterocycl. Chem., 1993, 30, 81-91.

[0072] For that purpose, mixtures of a (substituted) indole, ketone or aldehyde and a dienophile are reacted in a suitable solvent, e.g. 1-butanol, toluene, DMF, DMSO or Tetralin, using acid catalysts, e.g. hydrochloric acid, trifluoroacetic acid, toluenesulfonic acid, etc. The ketone or aldehyde component can also serve as solvent. The mixture is heated for several hours at a temperature of from 50° C. to 140° C. The resulting tetrahydrocarbazoles are filtered off and washed, or precipitated from the solvent with cold n-hexane and filtered off. Some of the substances are also obtained by concentrating the reaction mixture by evaporation.

[0073] The course of the reaction can be represented schematically as follows: 143

[0074] The tetrahydrocarbazoles obtained in that manner are generally obtained in the form of race-mates and are mainly in the cis stereochemical form. Some compounds also form trans stereochemical isomers.

[0075] The invention relates also to the process for the preparation of those compounds.

[0076] The tetrahydrocarbazoles according to the invention exhibit pronounced antimicrobial activity, especially against pathogenic gram-positive and gram-negative bacteria and against bacteria of the skin flora, and also against yeasts and moulds. They are accordingly especially suitable for disinfection, deodorisation, and for the general and antimicrobial treatment of the skin and mucosa, and integumentary appendages (hair), especially for the disinfection of hands and wounds.

[0077] The compounds are accordingly suitable as antimicrobial active ingredients and as preservatives in personal care preparations, such as shampoos, bath additives, hair care products, liquid and solid soaps (based on synthetic surfactants and salts of saturated and/or unsaturated fatty acids), lotions and creams, deodorants, other aqueous or alcoholic solutions, e.g. cleansing solutions for the skin, moist wipes, oils or powders.

[0078] The invention accordingly relates also to a personal care preparation comprising at least one compound of formula (1) or (2) and cosmetically tolerable carriers or adjuvants.

[0079] The personal care preparation according to the invention contains from 0.01 to 15% by weight, preferably from 0.1 to 10% by weight, based on the total weight of the composition, of a compound of formula (1) or (2) and cosmetically tolerable adjuvants.

[0080] Depending upon the form of the personal care preparation, it comprises, in addition to the compound of formula (1) or (2), further constituents, such as sequestering agents, colourings, perfume oils, thickening or solidifying agents (consistency regulators), emollients, UV-absorbers, skin protective agents, antioxidants, additives that improve the mechanical properties, such as dicarboxylic acids and/or aluminium, zinc, calcium or magnesium salts of C14-C22 fatty acids and, optionally, preservatives.

[0081] The personal care preparation according to the invention may be in the form of a water-in-oil or oil-in-water emulsion, an alcoholic or alcohol-containing formulation, a vesicular dispersion of an ionic or non-ionic amphiphilic lipid, a gel, a solid stick or an aerosol formulation.

[0082] As a water-in-oil or oil-in-water emulsion the cosmetically tolerable adjuvant contains preferably from 5 to 50% of an oil phase, from 5 to 20% of an emulsifier and from 30 to 90% water. The oil phase may comprise any oil suitable for cosmetic formulations, for example one or more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fatty acid ester or a fatty alcohol.

[0083] Preferred mono- or poly-ols are ethanol, isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.

[0084] Cosmetic formulations according to the invention are used in various fields. There come into consideration, for example, especially the following preparations:

[0085] skin-care preparations, e.g. skin-washing and cleansing preparations in the form of tablet-form or liquid soaps, synthetic detergents or washing pastes,

[0086] bath preparations, e.g. liquid (foam baths, milks, shower preparations) or solid bath preparations, e.g. bath cubes and bath salts;

[0087] skin-care preparations, e.g. skin emulsions, multi-emulsions or skin oils;

[0088] cosmetic personal care preparations, e.g. facial make-up in the form of day creams or powder creams, face powder (loose or compressed), rouge or cream make-up, eyecare preparations, e.g. eyeshadow preparations, mascara, eyeliner, eyecreams or eye-fix creams; lip-care preparations, e.g. lipsticks, lip gloss, lip contour pencils, nail-care preparations, such as nail varnish, nail varnish removers, nail hardeners or cuticle removers;

[0089] intimate hygiene preparations, e.g. intimate washing lotions or intimate sprays;

[0090] foot-care preparations, e.g. foot baths, foot powders, foot creams or foot balsams, special deodorants and antiperspirants or callus-removing preparations;

[0091] light-protective preparations, such as sun milks, lotions, creams, oils, sun-blocks or tropicals, pre-tanning preparations or after-sun preparations;

[0092] skin-tanning preparations, e.g. self-tanning creams;

[0093] depigmenting preparations, e.g. preparations for bleaching the skin or skin-lightening preparations;

[0094] insect repellents, e.g. insect-repellent oils, lotions, sprays or sticks;

[0095] deodorants, such as deodorant sprays, pump-action sprays, deodorant gels, sticks or roll-ons;

[0096] antiperspirants, e.g. antiperspirant sticks, creams or roll-ons;

[0097] preparations for cleansing and caring for blemished skin, e.g. synthetic detergents (solid or liquid), peeling or scrub preparations or peeling masks;

[0098] hair-removal preparations in chemical form (depilation), e.g. hair-removing powders, liquid hair-removing preparations, cream- or paste-form hair-removing preparations, hair-removing preparations in gel form or aerosol foams;

[0099] shaving preparations, e.g. shaving soap, foaming shaving creams, non-foaming shaving creams, foams and gels, preshave preparations for dry shaving, aftershaves or aftershave lotions;

[0100] fragrance preparations, e.g. fragrances (eau de Cologne, eau de toilette, eau de perfume, perfume de toilette, perfume), perfume oils or perfume creams;

[0101] dental care, denture-care and mouth-care preparations, e.g. toothpastes, gel toothpastes, tooth powders, mouthwash concentrates, anti-plaque mouthwashes, denture cleaners or denture fixatives;

[0102] cosmetic hair-treatment preparations, e.g. hair-washing preparations in the form of shampoos and conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-structuring preparations, e.g. hair-waving preparations for permanent waves (hot wave, mild wave, cold wave), hair-straightening preparations, liquid hairsetting preparations, hair foams, hairsprays, bleaching preparations, e.g. hydrogen peroxide solutions, lightening shampoos, bleaching creams, bleaching powders, bleaching pastes or oils, temporary, semi-permanent or permanent hair colourants, preparations containing self-oxidising dyes, or natural hair colourants, such as henna or camomile.

[0103] An antimicrobial soap has, for example, the following composition:

[0104] 0.01 to 5% by weight of a compound of formula (1) or (2),

[0105] 0.3 to 1% by weight titanium dioxide,

[0106] 1 to 10% by weight stearic acid,

[0107] ad 100% soap base, e.g. a sodium salt of tallow fatty acid or coconut fatty acid, or glycerol.

[0108] A shampoo has, for example, the following composition:

[0109] 0.01 to 5% by weight of a compound of formula (1) or (2),

[0110] 12.0% by weight sodium laureth-2-sulfate,

[0111] 4.0% by weight cocamidopropylbetaine,

[0112] 3.0% by weight NaCl and

[0113] water ad 100%.

[0114] A deodorant has, for example, the following composition:

[0115] 0.01 to 5% by weight of a compound of formula (1) or (2),

[0116] 60% by weight ethanol,

[0117] 0.3% by weight perfume oil, and

[0118] water ad 100%.

[0119] The invention relates also to an oral composition comprising

[0120] 0.01 to 15% by weight, based on the total weight of the composition, of a compound of formula (1) or (2), and orally tolerable adjuvants.

[0121] Example of an oral composition:

[0122] 10% by weight sorbitol,

[0123] 10% by weight glycerol,

[0124] 15% by weight ethanol,

[0125] 15% by weight propylene glycol,

[0126] 0.5% by weight sodium lauryl sulfate,

[0127] 0.25% by weight sodium methylcocyl taurate,

[0128] 0.25% by weight polyoxypropylene/polyoxyethylene block copolymer,

[0129] 0.10% by weight peppermint flavouring,

[0130] 0.1 to 0.5% by weight of a compound of formula (1) or (2) and

[0131] 48.6% by weight water.

[0132] The oral composition according to the invention may be, for example, in the form of a gel, a paste, a cream or an aqueous preparation (mouthwash).

[0133] The oral composition according to the invention may also comprise compounds that release fluoride ions which are effective against the formation of caries, for example inorganic fluoride salts, e.g. sodium, potassium, ammonium or calcium fluoride or organic fluoride salts, e.g. amine fluorides, which are known under the trade name Olafluor.

[0134] The tetrahydrocarbazoles of formula (1) or (2) used according to the invention are also suitable for treating, especially preserving, textile fibre materials. Such materials are undyed and dyed or printed fibre materials, e.g. of silk, wool, polyamide or polyurethanes, and especially cellulosic fibre materials of all kinds. Such fibre materials are, for example, natural cellulose fibres, such as cotton, linen, jute and hemp, as well as cellulose and regenerated cellulose. Preferred suitable textile fibre materials are made of cotton.

[0135] The tetrahydrocarbazoles according to the invention are suitable also for treating, especially imparting antimicrobial properties to or preserving, plastics, e.g. polyethylene, polypropylene, polyurethane, polyester, polyamide, polycarbonate, latex, etc. Fields of use therefore are, for example, floor coverings, plastics coatings, plastics container and packaging materials; kitchen and bathroom utensils (e.g. brushes, shower curtains, sponges, bathmats), latex, filter materials (air and water filters), plastics articles used in the field of medicine, e.g. dressing materials, syringes, catheters, etc., so-called “medical devices”, gloves and mattresses.

[0136] Paper, for example papers used for hygiene purposes, may also be provided with antimicrobial properties using the tetrahydrocarbazoles according to the invention.

[0137] It is also possible for nonwovens, e.g. nappies/diapers, sanitary towels, panty liners, and cloths for hygiene and household uses, to be provided with antimicrobial properties in accordance with the invention.

[0138] The tetrahydrocarbazoles of formula (1) or (2) are also used in washing and cleaning formulations, e.g. in liquid or powder washing agents or softeners.

[0139] The tetrahydrocarbazoles of formula (1) or (2) can be used especially in household and general-purpose cleaners for cleaning and disinfecting hard surfaces.

[0140] A cleaning preparation has, for example, the following composition:

0.01 to 5% of a compound of formula (1) or (2),
3.0%       octyl alcohol 4EO,
1.3%       fatty alcohol C8-C10 polyglucoside,
3.0%       isopropanol,
ad 100%    water.

[0141] In addition to preserving cosmetic and household products, the preservation of technical products, the provision of technical products with antimicrobial properties and use as a biocide in technical processes are also possible, for example in paper treatment, especially in paper treatment liquors, print thickeners of starch or of cellulose derivatives, surface coatings and paints.

[0142] The tetrahydrocarbazoles of formula (1) or (2) according to the invention are suitable also for the antimicrobial treatment of wood and for the antimicrobial treatment of leather, the preservation of leather and the provision of leather with antimicrobial properties.

[0143] The compounds according to the invention are also suitable for the protection of cosmetic products and household products from microbial damage.

[0144] The tetrahydrocarbazoles according to the invention are suitable also as medicaments for the treatment of bacterial infections for oral, intravenous, subcutaneous or parenteral administration of the active ingredient.

[0145] The invention accordingly relates also to a medicament comprising a compound of formula (1) or (2) and therapeutically tolerable adjuvants, for the treatment of bacterial infections.

[0146] The following Examples illustrate the invention.

[0147] General Procedure for the Preparation of the Tetrahydrocarbazoles According to the Invention:

[0148] The appropriate (substituted) indole (compound (I)) (1 mmol) is dissolved with (substituted) maleimide (compound (IV) (1.2 mmol) and an aldehyde/ketone (compound (II) (2 mmol) in 1-butanol (1 ml).

[0149] There is then added to the mixture aqueous hydrochloric acid (2N; 50 μl; 0.1 mmol) or, in the case of piperidones, concentrated hydrochloric acid (32%; 220 μl; 1.1 mmol). The mixture is then heated at 95° C. for 3 hours.

[0150] After cooling to 25° C., the resulting tetrahydrocarbazole (compound (1)) is precipitated with n-hexane (3 ml).

[0151] After filtration, the filtrate is cooled to 5° C. in order to obtain further crystals. The combined crystals are washed with n-hexane/ethyl acetate and dried in vacuo.

[0152] All the compounds, that is to say the compounds of formulae (9) to (181), are characterised by LC-MS (for yields, see Table 1). Some of the compounds are analysed by NMR spectroscopy. The compounds are obtained in the form of mixtures of isomers (racemates or exo/endo isomers).

PREPARATION EXAMPLES

Example 1

10-Bromo-3a,3b,4,5,6,7,8,8a,13,13b-decahydro-1H-cyclohepta[c]pyrrolo-[3,4-a]carbazole-1.3(2H)-dione (compound of formula (32)

[0153] 144

[0154] Yield: 72%

[0155] LC-MS: [M+H]+=386 (79Br)

[0156] NMR Data:

[0157] For reasons of clarity, the numbering used is not in accordance with IUPAC. 145

	Assignment	d1H [ppm]	d13C [ppm]
	OC-1	—	176.5
	HN-1	approx. 11	—
	OC-3	—	180.4
	HC-4	3.40	44.1
	HC-5	2.32	37.6
	H2C-6	1.82	28.1
		1.58
	H2C-7	1.88	30.4
		1.28
	H2C-8	1.74	24.2
		1.41
	H2C-9	2.39	27.3
		1.81
	H2C-10	1.73	30.4
	HC-11	3.12	35.5
	C-12	—	114.1
	C-13	—	127.6
	HC-14	7.48	120.3
	C-15	—	111.0
	HC-16	7.16	123.6
	HC-17	7.31	113.5
	C18	—	135.7
	HN-19	11.11	—
	C-20	—	128.8
	HC-21	4.09	41.6
	3JH-21,H-4=7.9Hz;
	3JH-4,H-5=5.1Hz

Example 2

2,6-Dimethyl-3b,4,5,6,7,7a,12,12b-octahydrobenzo[c]pyrrolo[3.4 a]carbazole-1,3(2H,3aH)-dione (compound of formula (117))

[0158] 146

[0159] Yield: 79%

[0160] LC-MS: [M+H]+=322

[0161] NMR Data:

[0162] For reasons of clarity, the numbering used is not in accordance with IUPAC. 147

	Isomer A	Isomer B
Assignment	δ1H [ppm]	δ13C [ppm]	δ1H [ppm]	δ13C [ppm]
OC-1	—	175.6a	—	175.9b
CH3—N-2	2.81	24.4	2.72	24.2
OC-3	—	178.6a	—	177.7b
HC-4	3.44	43.9	3.45	44.3
HC-5	2.35	33.8	1.58	40.8
H2C-6	1.99	26.1	2.33	29.2
	1.73		1.83
H2C-7	1.85	30.2	1.80	35.1
	1.51		0.96
H2C-8	1.67	30.8	1.58	31.7
H3C-9	0.79	21.8	0.96	22.5
H2C-10	1.86	37.7	2.84	40.0
	0.96		0.91
HC-11	3.02	33.6	2.56	34.9
C-12	—	113.9	—	113.4
C-13	—	125.8	—	125.5
HC-14	7.46	118.2c	7.61	119.9c
HC-15	6.93	118.3	6.89	118.3
HC-16	7.02d	120.9	7.00d	120.7
HC-17	7.34	111.4	7.32	111.4
C18	—	136.9	—	136.9
HN-19	10.94	—	11.06	—
C-20	—	126.6	—	127.6
HC-21	4.21	43.8	4.23	42.3

Example 3

9-Bromo-6-methyl-3b,4,5,6,7,7a,12,12b-octahydrobenzo[c]pyrrolo-[3,4-a]carbazole-1,3(2H,3aH)-dione (compound of formula (70))

[0163] 148

[0164] Yield: 71%

[0165] LC-MS: [M+H]+=386 (79Br) 149

	Isomer A	Isomer B
Assignment	δ1H [ppm]	δ13C [ppm]	δ1H [ppm]	δ13C [ppm]
OC-1	—	175.6a	—	175.9b
CH3—N-2	2.81	24.4	2.72	24.2
OC-3	—	178.6a	—	177.7b
HC-4	3.44	43.9	3.45	44.3
HC-5	2.35	33.8	1.58	40.8
H2C-6	1.99	26.1	2.33	29.2
	1.73		1.83
H2C-7	1.85	30.2	1.80	35.1
	1.51		0.96
H2C-8	1.67	30.8	1.58	31.7
H3C-9	0.79	21.8	0.96	22.5
H2C-10	1.86	37.7	2.84	40.0
	0.96		0.91
HC-11	3.02	33.6	2.56	34.9
C-12	—	113.9	—	113.4
C-13	—	125.8	—	125.5
HC-14	7.46	118.2c	7.61	119.9c
HC-15	6.93	118.3	6.89	118.3
HC-16	7.02d	120.9	7.00d	120.7
HC-17	7.34	111.4	7.32	111.4
C18	—	136.9	—	136.9
HN-19	10.94	—	11.06	—
C-20	—	126.6	—	127.6
HC-21	4.21	43.8	4.23	42.3

Example 3

9-Bromo-6-methyl-3b,4,5,6,7,7a,12,12b-octahydrobenzo[c]pyrrolo-[3,4-a]carbazole-1,3(2H,3aH)-dione (compound of formula (70))

[0166] 150

[0167] Yield: 71%

[0168] LC-MS: [M+H]+386 (79Br)

[0169] NMR Data:

[0170] For reasons of clarity, the numbering used is not in accordance with IUPAC.

	Assignment	δ1H [ppm]	δ13C [ppm]
	OC-1	—	176.8
	HN-1	11.06	—
	OC-3	—	179.1
	HC-4	3.43	?
	HC-5	1.50	40.6
	H2C-6	2.26	29.1
		1.75
	H2C-7	1.76	35.1
		0.94
	H2C-8	1.56	31.7
	H3C-9	0.96	22.6
	H2C-10	2.75	39.7
		0.85
	HC-11	2.57	34.7
	C-12	—	113.2
	C-13	—	127.3
	HC-14	7.76	121.8
	C-15	—	110.8
	HC-16	7.13	123.1
	HC-17	7.29	113.3
	C18	—	135.5
	HN-19	11.26	—
	C-20	—	129.8
	HC-21	4.14	42.9
	3JH-21,H-4=7.9Hz
	3JH-4,H-5=4.1Hz

[0171] The remaining compounds listed in Table 1 can be prepared in analogous manner.

[0172] 4. Microbiological Test Results

[0173] Nutrient:

[0174] Casein/soybean flour peptone bouillon for the preparation of pre-cultures of the test bacteria and yeast.

[0175] Mycological slant agar for the pre-culture of moulds

[0176] Examples of Test Organisms:

Staphylococcus hominis DMS 20328 Staphylococcus epidermidis
Escherichia coli NCTC 8196       ATCC 12228
Corynebacterium xerosis ATCC 373 P. ovale ATCC 14521
Enterococcus hirae ATCC 10541    Actinomyces viscosus DSM 43329
Micrococcus luteus ATCC 9341     Porphyromonas gingivalis DSM 20709
Candida albicans ATCC 10259      Selenomonas artemidis ATCC 43528
Staphylococcus aureus (methicillin-resistant) NCTC Streptococcus mutans ATOC 25175
11940                            Streptococcus sobrinus DSM 20742
Staphylococcus aureus (methicillin-resistant) Epidermophyton floccosum DSM 10709
NCTC 12493
Staphylococcus aureus (penicillin-resistant) Tr. mentagrophytes ATCC 9533
NCTC 10443                       Trichophyton rubrum DSM 4167
Staphylococcus aureus (rifampicin-resistant) Trichoderma longibrachiatum
NCTC 10703                       DSM 768
Propionibacterium acnes ATCC 25746 Aspergillus niger ATCC 6175

[0177] Procedure:

[0178] The test substances are predissolved in dimethyl sulfoxide (DMSO) and tested in a dilution series of 1:2.

[0179] Bacteria and yeast are cultured overnight in CASO bouillon, the mould is cultured over-night on mycological slant agar, and washed off with 10 ml of 0.85% sodium chloride solution (+0.1% TritonX-100).

[0180] All the test organisms are adjusted to an organism count of 1-5×106 CFU/ml using 0.85% sodium chloride solution.

[0181] The test substances are pre-pipetted into microtitre plates in an amount of 8 μl per well.

[0182] Pre-diluted organism suspensions are diluted 1:100 in CASO bouillon (bacteria and yeast) or Sabouraud 2% glucose bouillon (mould) and are added in an amount of 192 μl per well to the test substances.

[0183] The test batches are incubated for 48 hours at 37° C. (bacteria and yeast) or for 5 days at 28° C. (mould).

[0184] After incubation, the growth is evaluated by reference to the turbidity of the test batches (optical density) at 620 nm in a microplate reader.

[0185] The minimum inhibitory concentration (MIC value) is the concentration of substance at which (compared with the growth of the control) an appreciable inhibition of growth (≦20% growth) of the test organisms is ascertained.

[0186] One microtitre plate is used for each test organism and substance concentration. All the substances are tested in duplicate.

[0187] The results are compiled in Table 2:

TABLE 2
Minimum inhibitory concentrations (MIC) in ppm of the compounds synthesised
against Staphylococcus hominis DMS 20328 and Escherichia coli
Compound	MIC [ppm]	MIC [ppm]	Compound	MIC [ppm]	MIC [ppm]
of formula	S. hominis	E. coli	of formula	S. hominis	E. coli
9	>36	>36	30	>120	>120
10	>48	>48	31	15	>120
11	>120	>120	32	3.75	>120
12	>120	>120	33	30	60
13	>120	>120	34	>120	>120
14	>120	>120	35	>120	>120
15	>120	>120	36	>120	>120
16	>120	>120	37	>120	>120
17	>120	>120	38	>120	>120
18	>120	>120	39	>120	>120
19	>120	>120	40	>120	>120
20	>120	>120	41	>120	>120
21	>120	>120	42	>120	>120
22	>120	>120	43	>120	>120
23	>64	>64	44	>120	>120
24	>120	>120	45	>120	>120
25	>120	>120	46	120	120
26	15	>120	47	>120	>120
27	60	>120	48	>120	>120
28	>120	>120	49	>120	>120
29	15	>120	50	>120	>120
51	>120	>120	80	120	>120
52	>120	>120	81	60	120
53	>120	>120	82	30	>120
54	>120	>120	83	>120	>120
55	>120	>120	84	120	>120
56	30	>120	85	>120	>120
57	>120	>120	86	120	>120
58	30	>120	87	15	120
59	>120	>120	88	>120	>120
60	120	>120	89	7.5	>120
61	3.75	>120	90	>120	>120
62	15	>120	91	>120	>120
63	7.5	>120	92	>120	>120
64	120	>120	93	60	>120
65	120	>120	94	>120	>120
66	>120	>120	95	>120	>120
67	>120	>120	96	>120	>120
68	>120	>120	97	120	>120
69	120	>120	98	>120	>120
70	15	>120	99	120	>120
71	60	>120	100	120	>120
72	120	>120	101	>120	>120
731	60	>120	102	60	>120
74	60	>120	103	>120	>120
75	30	>120	104	>120	>120
76	>120	>120	105	>120	>120
77	15	>120	106	3.75	>120
78	60	>120	107	120	>120
79	120	>120	108	>120	>120
109	>120	>120	138	>120	>120
110	120	>120	139	>120	>120
111	60	>120	140	120	>120
112	>120	>120	141	>120	>120
113	>120	>120	142	>120	>120
114	>120	>120	143	>120	>120
115	60	>120	144	>120	>120
116	120	>120	145	>120	>120
117	>120	>120	146	>120	>120
118	>120	>120	147	>120	>120
119	>120	>120	148	>120	>120
120	30	>120	149	120	120
121	>120	>120	150	>120	>120
122	>120	>120	151	>120	>120
123	>120	120	152	120	>120
124	>120	>120	153	>120	>120
125	>120	>120	154	>120	>120
126	>120	>120	155	>120	>120
127	60	>120	156	>120	>120
128	>120	>120	157	>120	>120
129	>120	>120	158	>120	>120
130	15	>120	159	7.5	120
131	>120	120	160	120	120
132	>120	>120	161	>120	>120
133	120	>120	162	120	>120
134	120	>120	163	>120	>120
135	>120	>120	164	>120	>120
136	>120	>120	165	120	>120
137	>120	>120	166	>120	>120
167	>120	>120
168	>120	>120
169	>120	>120
170	>120	>120
171	>120	>120
172	>120	>120
173	>120	>120
174	30	>120
175	>120	>120
176	>120	>120
177	120	120
178	>120	>120
179	>120	>120
180	>120	>120
181	>120	>120

[0188]

TABLE 3
Further minimum inhibitory concentrations (MIC) in ppm of selected compounds
(MIC values in ppm)
	Compound of formula
Microorganism	61	63	70	87	89	106
Staphylococcus hominis DSM	3.75	7.5	15	15	7.5	3.75
20328
Staphylococcus epidermidis	≦3.75	≦3.75	15	15	≦3.75	≦3.75
ATCC 12228
Corynebacterium xerosis	≦3.75	≦3.75	7.5	7.5	≦3.75	≦3.75
ATCC 373
Enterococcus hirae	7.5	7.5	60	30	>120	>120
ATCC 10541
Micrococcus luteus ATCC 9341	≦3.75	≦3.75	15	15	≦3.75	≦3.75
Candida albicans ATCC 10259	>120	>120	>120	>120	>120	>120

[0189]

TABLE 4
Minimum inhibitory concentrations (MIC) in ppm of compound
(32) against methicillin, penicillin-resistant Staphylococci and
other microorganisms
>(MIC values in ppm)
Compound of formula (32)
Microorganism		Microorganism
Staphylococus aureus ATCC 9144	5.0 ppm	P. ovale ATCC 14521	>10 ppm
Staphylococcus hominis DSM 20328	5.0 ppm	Actinomyces viscosus	6.25 ppm
		DSM 43329
Staphylococcus aureus (methicillin-	5.0 ppm	Porphyromonas gingivalis	3.125 ppm
resistant) NCTC 11940		DSM 20709
Staphylococcus aureus (methicillin-	5.0 ppm	Selenomonas artemidis	50.0 ppm
resistant) NCTC 12493		ATCC 43528
Staphylococcus aureus (penicillin-	5.0 ppm	Streptococcus mutans	5.0 ppm
resistant) NCTC 10443		ATCC 25175
Staphylococcus aureus (rifampicin-	5.0 ppm	Streptococcus sobrinus	6.25 ppm
resistant) NCTC 10703		DSM 20742
S. epidermidis ATCC 12228	10 ppm	Candida albicans ATCC	>10 ppm
		10259
Corynebacterium xerosis ATCC 373	5.0 ppm	Epidermophyton floccosum	5.0 ppm
		DSM 10709
Micrococcus luteus ATCC 9341	5.0 ppm	Tr. mentagrophytes ATCC	10 ppm
		9533
Enterococcus hirae ATCC 10541	>10 ppm	Trichophyton rubrum DSM	10 ppm
		4167
Propionibacterium acnes ATCC	6.25 ppm	Trichoderma longibrachiatum	>10 ppm
25746		DSM 768
		Aspergillus niger ATCC	>10 ppm
		6175

[0190]

TABLE 5
Minimum inhibitory conc ntrations (MIC) in ppm of
selected synthesised compounds against
selected test organisms
Compound
of	MIC [ppm]	MIC [ppm]	MIC [ppm]	MIC [ppm]
formula	S. hominis	E. coil	P. aeruginosa	A. niger
182	>120	>120	>120	>120
183	15	>120	>120	>120
184	>120	>120	>120	>120
185	>120	>120	>120	>120
186	>120	>120	120	>120
187	30	>120	60	>120
188	15	>120	>120	>120
189	15	120	>120	>120
190	>120	>120	>120	>120
191	7.5	>120	>120	120
192	7.5	>120	>120	>120
193	>120	60	>120	>120
194	7.5	>120	>120	>120
195	15	>120	>120	>120
196	7.5	>120	>120	>120
197	>120	>120	120	>120
198	>120	>120	>120	>120
199	120	>120	>120	>120
200	>120	>120	120	>120
201	>120	>120	60	>120
202	60	>120	120	>120
203	>120	>120	>120	>120
204	15	120	60	>120
205	7.5	>120	120	>120
206	7.5	>120	60	>120
207	>120	>120	120	>120
208	15	>120	>120	>120
209	30	>120	120	>120
210	120	>120	120	>120
211	>120	120	120	>120
212	120	>120	>120	>120
213	>120	>120	>120	>120
214	15	120	120	120
215	30	60	120	>120
216	15	120	120	120
217	<3.75	>120	>120	>120
218	15	>120	120	>120
219	>120	>120	>120	>120
220	15	>120	>120	>120
221	15	>120	60	>120
222	120	120	>120	>120
223	>120	>120	60	>120
224	>120	>120	120	>120
225	120	>120	120	>120
226	120	120	>120	>120
227	>120	>120	>120	>120
228	15	>120	>120	>120
229	>120	>120	>120	>120
230	120	>120	120	>120
231	120	>120	120	>120
232	>120	>120	>120	>120
233	15	>120	120	>120
234	>120	>120	120	>120
235	120	>120	>120	>120
236	>120	>120	120	>120
237	>120	>120	120	>120
238	>120	>120	>120	>120
239	120	120	120	>120

Claims

1. A compound of formula

2. A compound of formula (1) or (2) according to claim 1, wherein R1 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20-alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkylcarbonyl, C1-C7alkoxycarbonyl, C3-C12cycloalkylcarbonyl, C3-C12-cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro, R2 is hydrogen; hydroxy; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; C1-C20alkoxy; C2-C20alkenyloxy; C2-C20alkynyloxy; halogen; cyano; C1-C7alkylcarbonyl; nitro; trifluoromethyl; or pentafluoroethyl; R3 and R4 are each independently of the other hydrogen; or C1-C20alkyl; or R3 and R4 denote a C2-C20alkylene radical; a C2-C20alkenylene radical; a C4-C20alkynylene radical; or a C3-C20alkylene radical interrupted by —N(R6)—, it being possible for such bivalent radicals to be further substituted by one or more C1-C20alkyl, C3-CO12cycloalkyl, C2-C20-alkenyl, C4-C12cycloalkenyl, C3-C20alkynyl, C4-C12cycloalkynyl, C1-C7alkoxycarbonyl, or phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12-cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro; R5 is hydrogen; hydroxy; C1-C20alkyl; C1-C20alkoxy; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1-C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro; R6 is hydrogen; C1-C20alkyl; C3-C12cycloalkyl; C2-C20alkenyl; C4-C12cycloalkenyl; C3-C20alkynyl; C4-C12cycloalkynyl; C1-C7alkoxycarbonyl; phenyl or phenyl-C1-C5alkyl each unsubstituted or substituted by C1-C5alkyl, C3-C12cycloalkyl, C1-C5alkoxy, C3-C12cycloalkoxy, halogen, carboxy, C1C7alkoxycarbonyl, C3-C12cycloalkoxycarbonyl, cyano, trifluoromethyl, pentafluoroethyl, amino, N,N-mono- or di-C1-C20alkylamino or by nitro; Q is —SO2—; —O—; or —(CO)—; X is —CH—; or —N—; m is from 1 to 3; and t is 0 or 1.

3. A compound according to claim 1 or claim 2, wherein R1 is hydrogen; C1-C20alkyl; phenyl or phenyl-C1-C5alkyl.

4. A compound according to any one of claims 1 to 3, wherein R1 is hydrogen; or C1-C5alkyl.

5. A compound according to any one of claims 1 to 4, wherein R2 is hydrogen; C1-C20alkyl; C1-C20alkoxy; or halogen.

6. A compound according to any one of claims 1 to 5, wherein R2 is hydrogen; C1-C5alkyl; C1-C5alkoxy; or halogen.

7. A compound according to any one of claims 1 to 6 that corresponds to formula

8. A compound according to claim 7, wherein T1 is a —(CH2)2-12— radical and R6 is hydrogen; or C1-C5alkyl.

9. A compound according to claim 8, wherein T1 is a —(CH2)3—, —(CH2l)4—, —(CH2)5—, or —(CH2)10— radical; and R6 is hydrogen; or C1-C5alkyl.

10. A compound according to any one of claims 1 to 9, wherein R5 is hydrogen; C1-C20alkyl; phenyl or phenyl-C1-C5alkyl.

11. A compound according to any one of claims 1 to 10, wherein R5 is hydrogen; C1-C5alkyl; or phenyl.

12. A compound according to any one of claims 1 to 11 of formula

13. A compound according to claim 12, wherein R6′, R6″ and R6 are each independently of the others hydrogen; C1-C20alkyl; C1-C7-alkoxycarbonyl; phenyl; or phenyl-C1-C5alkyl.

14. A compound according to claim 13, wherein R6′, R6″ and R6 are each independently of the others hydrogen; C1-C5alkyl; C1-C7-alkoxycarbonyl; phenyl or benzyl.

15. A compound according to any one of claims 1 to 14 that corresponds to formula

16. A process for the preparation of a compound of formula (1) or (2) according to claim 1, wherein an indole compound (I), a keto or aldehyde compound of formula (II) and a dienophile of formula (IV) or (V), respectively, are reacted in a suitable solvent using an acid catalyst at a temperature of from 50° C. to 140° C. to form a compound of formula (1) or (2), respectively, in accordance with the following scheme:

17. Use of a compound of formula (1) or (2) according to claim 1 in the antimicrobial treatment, deodorisation and disinfection of the skin, mucosa and hair.

18. Use according to claim 17, wherein the compound of formula (1) or (2) is used for disinfection and deodorisation.

19. Use of a compound of formula (1) or (2) according to claim 1 in the treatment of textile fibre materials.

20. Use according to claim 19, wherein the compound of formula (1) or (2) is used for preservation.

21. Use of a compound of formula (1) or (2) according to claim 1 in washing and cleaning formulations.

22. Use of a compound of formula (1) or (2) according to claim 1 in imparting antimicrobial properties to and preserving plastics, paper, nonwovens, wood or leather.

23. Use of a compound of formula (1) or (2) according to claim 1 in imparting antimicrobial properties to and preserving technical products, especially print thickeners of starch or of cellulose derivatives, surface coatings and paints.

24. Use of a compound of formula (1) or (2) according to claim 1 as a biocide in technical processes, especially in paper treatment.

25. A personal care preparation comprising from 0.01 to 15% by weight, based on the total weight of the composition, of a compound of formula (1) or (2) according to claim 1 and cosmetically tolerable adjuvants.

26. An oral composition comprising from 0.01 to 15% by weight, based on the total weight of the composition, of a compound of formula (1) or (2) according to claim 1 and orally tolerable adjuvants.

27. A medicament comprising a compound of formula (1) or (2) according to claim 1 and therapeutically tolerable adjuvants, for the treatment of bacterial infections.