Chemistry of polyhalogenated nitrobutadienes, part 9: Acyclic and heterocyclic nitroenamines and nitroimines from 2-nitroperchlorobuta-1,3-diene

Chemistry of Polyhalogenated Nitrobutadienes, Part 9:

Acyclic and Heterocyclic Nitroenamines and Nitroimines

from 2-Nitroperchlorobuta-1,3-diene

Viktor A. Zapol’skii^a, Jan C. Namyslo^a, Mimoza Gjikaj^b, and Dieter E. Kaufmann^a

^aInstitute of Organic Chemistry, Clausthal University of Technology, Leibnizstraße 6,

38678 Clausthal-Zellerfeld, Germany

^bInstitute of Inorganic and Analytical Chemistry, Clausthal University of Technology,

Paul-Ernst-Straße 4, 38678 Clausthal-Zellerfeld, Germany

Reprint requests to Prof. Dr. D. E. Kaufmann. Fax: +49-5323-722834.

E-mail: dieter.kaufmann@tu-clausthal.de

Z. Naturforsch. 2010, 65b, 843 – 860; received May 6, 2010

Various amino, diamino, aminothio, or benzotriazolo compounds derived from the exceedingly

versatile 2-nitroperchlorobutadiene (1) gave structurally interesting and physiologically promising

nitro-enamines, -imines, -amidines, and hydrazines as well as ring closure reaction products, e. g.

pyrimidines and pyrazoles. Most of these reactions turned out to be highly selective with good to

very good yields. The structure of the pyrazole precursor (E,E)-1-(benzotriazol-1-yl)-4,4-dichloro-3-

(4-ethoxyphenylamino)-1-(4-ethoxyphenylimino)-2-nitrobut-2-ene (30), due to its exceptional sub-

stitution pattern, was evidenced by single-crystal X-ray diffraction analysis.

Key words: Nitro Compounds, Nucleophilic Substitution, Pyrimidines, Pyrazoles, Betaines,

Click Chemistry

Introduction

ﬁty is caused by the fact that the LUMO of 1 is lo-

cated preferentially at the dihalogeno-nitrovinyl frag-

ment, and to an extent of 67 – 85 % at the C-1 carbon

atom [1d]. Therefore, the ﬁrst nucleophilic substitution

reaction usually takes place at the C-1 position of 1 and

proceeds stereospeciﬁcally with respect to the conﬁg-

uration of the double bonds. The ease of the second,

hence twofold substitution at the C-1 atom is probably

due to an extraordinary high electrophilicity of the as-

sumed imide chloride intermediate A shown in Scheme

1. In fact, the reaction at this imine-type carbon atom is

preferred over the nucleophilic attack at the β-carbon

atom of the nitrodichlorovinylene moiety and exclu-

sively leads to the 1,1-bisamines 2 – 7 (Scheme 1).

The substructure of a nitro-substituted enamine

within compounds 2 – 7 should enable a stabilization

caused by a strong hydrogen bond between an oxygen

atom of the nitro group and the single proton at the

aniline nitrogen atom as shown in Fig. 1 (framed struc-

ture), a behavior typical of such enamines [6, 7].

In the course of our studies concerning polyhalo-

genated nitrodienes, in many cases 2-nitroperchloro-

butadiene (1) [1] or nitrotrichloroethylene [2] proved

themselves as appropriate precursors for a diverse va-

riety of synthetically and/or physiologically interest-

ing chemical compounds. Especially diene 1 is often

the starting material of choice, due to its stepped re-

activity in S_NVin processes. Thus, applying selective

and mild reactions, this diene enables click chemistry-

type syntheses [3]. In the present paper, we mainly fo-

cus on recent progress in the syntheses of acyclic and

heterocyclic nitro-enamines and -imines [4, 5], such as

nitropyrimidines or nitropyrazoles, or benzoannelated

nitrovinylidene bisheterocycles.

Results and Discussion

The vinylic S_Nreaction of 2-nitroperchlorobuta-

diene (1) with at least four equivalents of an ani-

line derivative that bears an electron-releasing group

Even though nitronate or iminic structures, in de-

(ERG/Hal) in 4-position of the phenyl ring selec- tail the depicted tautomeric amidines, are plausible

tively affords the corresponding 1,1-bis(arylamino)- to occur and have been previously proven by NMR

butadienes 2 – 7 with up to 95 % yield. The regiospeci- spectroscopy in case of the reaction of 1 with ani-

c

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

Scheme 1.

R = para-substituted phenyl as shown in Scheme 1.

Fig. 1. Tautomers of enamines 2 – 7.

line and o-chloroaniline [8], in the present case the by the aniline derivative, but in the second step, the

proton spectra gave no characteristic signal of such a imidoyl chloride unit within 1 then preferentially re-

deshielded methine proton that is located in a termi- acts with an adjacent oxygen atom of the nitro group,

nal dichloromethyl group. In contrast, applying less i. e. in competition with the electron-deﬁcient anilines.

basic anilines with electron withdrawing groups in 4- Further mechanistic aspects have been previously pub-

position of the phenyl ring, N-tetrachloroallylidene- lished by our group [9], but herein it should be ex-

N^ꢀ-arylhydrazines were obtained instead of the afore- plicitly stated that subsequent to the mentioned nu-

mentioned 1,1-bisamination products. The reaction cleophilic attack the C-1 carbon atom of the butadi-

starts again with the initial nucleophilic substitution ene derivative 1 is lost in the form of carbon dioxide.

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

845

Scheme 2.

Thus, regarding the syntheses in this paper, the con-

version of 1 with 4-nitroaniline and 4-cyanoaniline af-

forded the N-(tetrachloroallylidene)-N^ꢀ-arylhydrazines

8 and 9, both with a C-3 backbone. The yields of these

N-perchloroallylidenederivatives were 63 % and 86 %,

respectively (Scheme 1).

The distinct electrophilic character of the C-1 car-

bon within 8 and 9, that is caused by electron with-

drawal to the C=N group and in addition to the chlo-

rine atom, prompted us to explore similar substitu-

tion reactions. Thereby, on application of aromatic or

aliphatic amines, the corresponding N-(1-amino-2,3,3-

trichloroallylidene)- N^ꢀ- arylhydrazines 10 – 13 were

obtained (yields 63 – 88 %; Scheme 1). Interestingly,

quite a number of aromatic hydrazones have been

found to exhibit extensive biological activity [10].

Fig. 2. Tautomers of 13.

tive 13 gave an inseparable 3 : 1 mixture as evidenced

by ¹H NMR. In principle, this course observation

should be expected because of the potential appearance

of two tautomers of 13 as depicted in Fig. 2.

In addition to the aforementioned conversions of 1

applying amines, we also became interested in extend-

ing the applicability to other nucleophiles, e. g. sulfur

compounds. As a promising example we started with

It is noteworthy that the hydrazones 10 – 12 are gen- 4-chlorothiophenol. The solventless reaction of buta-

erated as single isomers, whereas the methoxy deriva- diene 1 with one equivalent of this sulfur-nucleophile

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

afforded the substitution product 14 in 78 % yield

(Scheme 2).

The exclusive formation of the (E)-isomer of 14 is

in accordance with the literature [11]. However, the oc-

currence of the (E)-isomer with the opposite conﬁg-

uration in 15 and 16, i. e. with the sulfur-substituent

in trans-position to the nitro group, is possible due

to free rotation around the single bond between C-1

and C-2 in the intermediate that is produced during the

attack of the N-nucleophile at the C-1 carbon atom.

These 1-amino-1-thiodienes 15 and 16 were obtained

in 80 % and 95 % yield, respectively, upon treatment of

the sulfur-substituted nitroperchlorobutadiene 14 with

amines. Comparing 15 with 16, it turned out that

within 16 the remaining amine proton additionally sup-

ports the (E)-conﬁguration by formation of a hydro-

gen bridge to the neighboring nitro substituent. Re-

cently, in an analogous way, the double bond conﬁg-

uration of similar nitrovinyl compounds had been as-

signed [12].

With the aim to synthesize N,N,S-substituted

dichloronitrobutadienes from 15 and 16, we went on

with S_NVin reactions. With regard to Pearson’s HSAB

concept [13], the monochloro-substituted α-carbon

atom within the trichloro-vinyl group of these amino-

thiodienes should give rise to an attack of further (rel-

atively weak) nucleophiles. Even though the applica-

tion of other, preferentially different sulfur nucleo-

philes is on our schedule, at ﬁrst we tested substi-

tution of this single chlorine atom of the Cl₂C=CCl

fragment by amines (Scheme 2). Two different types

of products appeared: the reaction of the morpholinyl

derivative 15 led to dichloronitrobutadiene 17 with the

expected N,N,S-substitution pattern, but conversion

of the chlorophenylaminodiene 16 afforded the corre-

sponding iminonitrobutene 18. Thus, the latter prod-

uct exhibits the most extended π system, i. e. from

the chlorophenyl moiety to the push-pull-substituted

oleﬁnic double bond. Also in this case, the struc-

tural assignment was unambiguouslyperformed apply-

ing NMR spectroscopy. In detail, even proton spec-

troscopy attested to the assumed structure, as the pro-

ton of the exterior HCCl₂fragment within 18 gave a

singlet at δ = 6.80 ppm and additionally a character-

istic increase of the one-bond C,H coupling constant

(from about 125 Hz to 182 Hz).

Fig. 3. Molecular structure of (E,E)-1-(benzotriazol-1-yl)-

4,4-dichloro-3-(4-ethoxyphenyl-amino)-1-(4-ethoxyphenyl-

imino)-2-nitrobut-2-ene (30) in the solid state.

zotriazole in tetrahydrofuran, whereupon the as-

pired twofold vinylic substitution at the C-1 car-

bon atom of nitrodiene 1 occurred with 72 % yield

(Scheme 2). Further conversions of the resulting

bis(benzotriazolyl)diene 19, each with one equivalent

of a different aniline derivative under mild condi-

tions, exclusively gave (E)-isomers of 1-arylamino-1-

benzotriazolylnitrobutadienes 20 – 24 in good to very

good yields up to 90 %. Again, the stereochemical out-

come should be due to the hydrogen bond between

the remaining aniline proton and the adjacent nitro

group. The desired N,N,N-substitution pattern subse-

quently was completed upon reaction of 20 – 24 with

two equivalents of various amines, i. e. more electron-

rich anilines with a 4-alkoxy substituent as well as ben-

zylamine, or non-aromatic amino compounds. Simi-

lar to the aforementioned product 18, also comprising

an imino group, a selection of (1E,3E)-1,3-diamino-

1-(benzotriazolyl)-4,4-dichloro-2-nitrobut-2-enes 25 –

35 was synthesized with yields ranging from 68 % to

94 %. Biological tests of these unique compounds are

underway. Some physiological potential can be ex-

pected, as even 2-nitrobut-2-enes have antiviral and

also cytotoxic properties [14]. Additionally, the pre-

cursor perchloronitrobutadiene1 was also proven to be

active against cancer cells [15]. Caused by the physi-

ological as well as synthetic key importance of these

1,1,3-triaminodichloronitro compounds, as an exam-

ple an X-ray structure analysis of compound 30 was

performed in addition to NMR-based structural assign-

ments (Fig. 3).

Aside from the N,N,S derivatives, we investigated

the access to the similar N,N,N-trisubstituted ni-

trobutadienes. Therefore, the precursor 1 was sub-

jected to reaction with four equivalents of ben-

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847

In contrast to previously synthesized acyclic prod- ric acid in case of 7 as the starting material (and

ucts, conversion of nitrobutadiene 7 or the nitrobutenes an aniline derivative in case of 25 – 35) which con-

28 and 30 with ﬁve equivalents of hydrazine hydrate sumes a further equivalent of hydrazine hydrate in the

in MeOH at room temperature in a multistep reaction former case, the dihydropyrazole C is formed. Sub-

sequence gave the interesting 5-amino-4-nitropyrazole sequently, the imine C tautomerizes to the aromatic

36, again as a single isomer (Scheme 3).

aminopyrazole D. The latter compound itself is then

converted by a further equivalent of hydrazine hy-

drate (and one more as acid scavenger) to the (hydrazi-

nomethyl)pyrazole E by substitution of one chlorine

atom of the terminal Cl₂CH group. The newly intro-

duced hydrazine group is transformed into the corre-

sponding hydrazone via HCl elimination, again sup-

ported by one equivalent of hydrazine hydrate. The

sequence ends up with the tautomerization to give 36

Scheme 3.

In Scheme 4 the assumed mechanistic pathway is (Scheme 4).

It turned out to be feasible to generate not only

pyrazoles, but also the rare and physiologically inter-

esting 5-nitropyrimidines [16] starting from appropri-

depicted with nitrobutadiene 7 as an example, together

with its amidine tautomer. However, this mechanism

should also reﬂect the behavior of the imines 28 and 30

(see Scheme 3), as well as further examples from ate benzotriazolylaminodienes,such as 21 – 24, and ac-

etamidine. In this case, at ﬁrst a bisimine 37 appeared,

which upon treatment with base (sodium hydride in

THF) then cyclized to the 5-nitropyrimidines 38 – 42

(Scheme 5).

In this context, the recently proposed mecha-

nism of this hetero ring formation [16b] can be reﬁned

the entire substance pool 25 – 35. In detail, the imino

moiety initially is attacked by one equivalent of hy-

drazine hydrate, releasing the NHAryl group (or the

benzotriazole in case of 25 – 30). The terminal amino

group of the hydrazine in intermediate A then forms

the pyrazolidine B. Upon elimination of hydrochlo-

Scheme 4.

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

Scheme 5.

Scheme 6.

Scheme 7.

in this paper, taking into account the now isolated starting from the aminobenzotriazolyldienes 20 – 24,

initial product 37. Thus, the previous assumption three equivalents of acetamidine hydrochloride, and

that the 1-benzotriazolyl group of such a 1-amino-1- four equivalents of the base (Scheme 7).

benzotriazolyl-3,4,4-trichloro-2-nitrobutadiene upon

treatment with an amidine reacts in the same way

as a corresponding 1,1-bisbenzotriazolyl compound,

was based on the isolation of the 1-amidinyl-1-

benzotriazolyl compound. However, in the present

case, the 3-chloro substituent reacts faster than the

1-benzotriazolyl group. Summarizing these new ﬁnd-

ings, initially a conjugated bisimine-enamine A is built

which then forms its tautomer 37. The terminal amino

group of the acetamidine moiety in 37 subsequently

attacks the C-1 position to give intermediate B, i. e. a

persubstituted 1,6-dihydropyrimidine. The mechanis-

tic pathway ends up with an aromatization step to give

the 5-nitropyrimidines 38 – 42 (Scheme 6).

Moreover, treatment of nitrodiene 1 with aromatic

ortho-substituted bisnucleophiles, such as 2-amino-

phenol, 2-aminothiophenol, or phenylenediamine, di-

rectly leads to bis-substitution at C-1 of the persubsti-

tuted butadiene. Good to very good yields of the re-

sulting benzoxazoline 43, benzthiazoline 44, and ben-

zimidazoline 45 up to 90% were obtained (Scheme 8).

Both of the mixed bisheterocycles, the N,O-derivative

43 as well as the N,S counterpart 44, appear as

one single isomer with (E)-conﬁguration, caused by

the aforementioned hydrogen bond stabilization. It

is noteworthy that 45 was previously synthesized

with only moderate yield and more laboriously, based

on 1,3,4,4-tetrachloro-2-nitro-1-(p-tolylthio)buta-1,3-

To perform these syntheses more efﬁciently, we diene [17] or bis(benzotriazole)diene 19, respectively.

tested a one-step method. Indeed, the pyrimidine This benzimidazoline exhibits herbicidal activity and

derivatives 38 – 42 were obtained in 47 to 69 % yield, acts as a model compound, when exploring ca-

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

849

Scheme 8.

seinolytic protease as target for herbicides or growth (also Bruker). ¹⁴N and ¹⁵N NMR spectra were measured

at their appropriate resonance frequency on the aforemen-

tioned spectrometers; ¹⁵N measurements were performed as

¹H,¹⁵N-HSQC or -HMBC NMR experiments (inverse detec-

tion). ¹H and ¹³C NMR spectra were referenced to the resid-

ual solvent peak: CDCl₃, δ = 7.26 (¹H), δ = 77.0 (¹³C);

[D₆]DMSO, δ = 2.50 (¹H), 39.7 (¹³C); [D₆]acetone, δ =

2.09 (¹H), 29.8 (¹³C). ¹⁴N and ¹⁵N NMR spectra were

referenced to nitromethane (0.0 ppm). In most cases, peak

assignments were accomplished by results of HSQC- and

HMBC-NMR experiments. Puriﬁcations were carried out by

means of column chromatography on silica gel 60 (Merck).

Petroleum ether as eluent had the boiling range 60 – 70 ^◦C. 2-

Nitropentachlorobuta-1,3-diene (1) was synthesized accord-

ing to the literature [19] from 2H-pentachlorobuta-1,3-diene

with a solution of 63 % HNO₃-98 % H₂SO₄(10 : 1) in 53 %

regulators [18].

With the hope to increase the physiological perfor-

mance, we also introduced the tertiary amine N,N-

dimethylaminopyridine into the bisheterocycles 43 –

45. Thus, under mild conditions at 0 ^◦C in MeOH, the

betaines 46 – 48 were synthesized in acceptable yields

of up to 64 % (Scheme 8).

By affording the novel and structurally interest-

ing cross-conjugated inner salts 46 – 48, once again

the broad synthetic applicability of 2-nitroperchloro-

butadiene, especially upon reaction with N- or S-

nucleophiles, is demonstrated. In conclusion, its selec-

tive and stepwise reactivity hitherto allowed for the

syntheses of various classes of chemical substances

and hundreds of compounds in our group [1, 2, 9, 16b],

partly with remarkable physiological activity. Apply-

ing click chemistry principles, further efﬁcient synthe-

ses of suchlike compounds appear feasible and promis-

ing.

◦

yield (b. p. 69 – 71 C/1 mbar). Trichloroacrolein was found

as a side product (8 %) and was separated by distillation (b. p.

57 – 58 ^◦C/12 mbar).

General method 1

3,4,4-Trichloro-N,N^ꢀ-bis(4-ﬂuorophenyl)-2-nitrobuta-1,3-

diene-1,1-diamine (2)

Experimental Section

A solution of 4-ﬂuoroaniline (5.00 g, 45 mmol) in 30 mL

Melting points were determined with a Bu¨chi appara- of MeOH was added dropwise to a solution of nitrodiene 1

◦

tus 520 and are uncorrected. Thin layer chromatography (2.71 g, 10 mmol) in 30 mL of MeOH at −40 C within

(tlc) was performed on Merck TLC-plates (aluminum based) 10 min. The resulting mixture was kept at the same tem-

silica gel 60 F 254. FTIR spectra were obtained with a perature for additional 20 min with stirring. After 6 h at

Bruker Vector 22 FT-IR in the range of 400 to 4000 cm⁻¹room temperature (r. t.) and subsequent cooling to 0 ^◦C,

(2.5 % pellets in KBr). Mass spectra were obtained on a 3 mL of concentrated hydrochloric acid was added. The

Hewlett Packard MS 5989B spectrometer, usually in direct resulting precipitate was ﬁltered off, washed with water

mode with electron impact (70 eV). In the case of chlori- (2 × 30 mL) and cold MeOH (10 mL), and then dried in

nated and brominated compounds, all peak values of molec- vacuo to give 2; yield: 3.62 g (8.61 mmol, 86 %); m. p. 170 –

ular ions as well as fragments refer to the isotope ³⁵Cl 172 ^◦C. – IR (KBr): ν = 3220, 3078, 2942, 1682, 1598, 1508,

and ⁷⁹Br. The elemental composition was conﬁrmed ei- 1310, 1240, 1123, 835, 697, 596, 540 cm⁻¹. – ¹H NMR

ther by combustion analysis or by high-resolution EI mass ([D₆]DMSO): δ = 10.23 (broad s, 2 H, NH), 7.38 – 6.90 (m,

1

spectrometry. All HRMS results were satisfactory in com- 8 H). – ¹³C NMR ([D₆]DMSO): δ = 159.8 (C-F, J_C,F

=

parison to the calculated accurate mass of the molecu- 242.5 Hz), 153.1 (C-1), 134.7 (CNH, ⁴J_C,F= 2.4 Hz), 126.1,

3

lar ion ( 2 ppm, R∼10000). ¹H NMR (600 MHz), ¹³C 122.9 (CCl=CCl₂), 124.8 (CH, J_C,F= 8.7 Hz), 116.1 (CH,

NMR (150 MHz): Avance III 600 MHz FT-NMR spectrom- ²J_C,F= 22.8 Hz), 109.3 (C-NO₂). – MS: m/z ( %) = 419 (3)

eter (Bruker, Rheinstetten, Germany); ¹H NMR (400 MHz), [M]⁺, 384 (15) [M–Cl]⁺, 373 (8) [M–NO₂]⁺, 290 (30) [M–

¹³C NMR (100 MHz): Avance 400 FT-NMR spectrometer C₂Cl₃]⁺, 274 (100) [M–C₂Cl₃–O]⁺. – HRMS ((+)-ESI):

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

m/z = 419.9881 (calcd. 419.9885 for C₁₆H₁₁Cl₃F₂N₃O₂, δ = 10.13 (broad s, 2 H, NH), 7.09 (d, J = 8.5 Hz, 4 H),

[M+H]⁺).

7.02 (d, J = 8.5 Hz, 4 H), 2.23 (s, 6 H, Me). – ¹³C NMR

([D₆]DMSO): δ = 152.4 (C-1), 136.0 (CNH), 134.4 (CMe),

129.6 (CH), 126.4, 122.2 (CCl=CCl₂), 121.9 (CH), 109.3

(C-NO₂), 20.7 (Me). – MS: m/z ( %) = 411 (4) [M]⁺, 376

(7) [M–Cl]⁺, 365 (4) [M–NO₂]⁺, 341 (63) [M–2Cl]⁺, 266

(37), 91 (100). – HRMS ((+)-ESI): m/z = 412.0381 (calcd.

412.0386 for C₁₈H₁₇Cl₃N₃O₂, [M+H]⁺).

3,4,4-Trichloro-N,N^ꢀ-bis(4-chlorophenyl)-2-nitrobuta-1,3-

diene-1,1-diamine (3)

General method 1, applying 4-chloroaniline and a tem-

◦

perature of 0 C instead of −40 C at the beginning; yield:

95 %; m. p. 179 – 181 ^◦C. – IR (KBr): ν = 3195, 3058, 2934,

1625, 1575, 1489, 1413, 1307, 1125, 1013, 827, 694, 589,

507 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ = 10.29 (broad

s, 2 H, NH), 7.36 (d, J = 8.8 Hz, 4 H), 7.15 (d, J =

8.8 Hz, 4 H). – ¹³C NMR ([D₆]DMSO): δ = 152.0 (C-1),

137.5 (CNH), 129.3 (CH), 129.2 (C_aryl-Cl), 126.0, 122.6

(CCl=CCl₂), 123.4 (CH), 110.0 (CNO₂). – MS: m/z ( %) =

451 (6) [M]⁺, 416 (9) [M–Cl]⁺, 405 (6) [M–NO₂]⁺, 322

(12) [M–C₂Cl₃]⁺, 111 (100). – HRMS ((+)-ESI): m/z =

451.9295 (calcd. 451.9294 for C₁₆H₁₁Cl₅N₃O₂, [M+H]⁺).

3,4,4-Trichloro-N,N^ꢀ-bis(4-ethoxyphenyl)-2-nitrobuta-1,3-

diene-1,1-diamine (7)

◦

General method 1, applying p-ethoxyaniline and −60 C

instead of −40 ^◦C at the beginning; yield: 70 %; m. p. 126 –

128 ^◦C. – IR (KBr): ν = 3229, 3038, 2937, 1618, 1576,

1509, 1477, 1295, 1247, 1170, 1120, 1047, 971, 922, 857,

825, 579, 548, 532 cm⁻¹. – ¹H NMR (CDCl₃): δ = 7.01 (d,

J = 8.8 Hz, 4 H), 6.77 (d, J = 8.8 Hz, 4 H), 3.97 (q, J =

7.0 Hz, 4 H, CH₂), 1.38 (t, J = 7.0 Hz, 6 H, Me); the NH pro-

ton was not detected due to chemical exchange reaction. –

¹³C NMR (CDCl₃): δ = 158.1 (C_aryl-O), 154.3 (C-1), 127.8

(CNH), 127.0, 124.0 (CCl=CCl₂), 126.8 (CH), 115.3 (CH),

108.9 (C-NO₂), 63.8 (CH₂), 14.6 (Me). – MS: m/z ( %) =

471 (4) [M]⁺, 436 (28) [M–Cl]⁺, 401 (27) [M–2Cl]⁺, 256

(45), 109 (100). – HRMS ((+)-ESI): m/z = 472.0587 (calcd.

472.0598 for C₂₀H₂₁Cl₃N₃O₄, [M+H]⁺).

N,N^ꢀ-Bis(4-bromophenyl)-3,4,4-trichloro-2-nitrobuta-1,3-

diene-1,1-diamine (4)

General method 1, starting from 4-bromoaniline; yield:

67 %; m. p. 171 – 173 ^◦C. – IR (KBr): ν = 3193, 3055,

2931, 1623, 1573, 1487, 1410, 1306, 1125, 1071, 1011, 822,

687, 580, 500 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ = 10.28

(broad s, 2 H, NH), 7.48 (d, J = 8.5 Hz, 4 H), 7.09 (d,

J = 8.5 Hz, 4 H). – ¹³C NMR ([D₆]DMSO): δ = 151.8

(C-1), 138.0 (CNH), 132.2 (CH), 126.0, 122.5 (CCl=CCl₂),

123.7 (CH), 117.3 (C-Br), 110.1 (C-NO₂). – MS: m/z ( %) =

539 [8) [M]⁺, 504 (17) [M–Cl]⁺, 471 (30), 396 (63), 109

(100). – HRMS ((+)-ESI): m/z = 539.8293 (calcd. 539.8284

for C₁₆H₁₁Br₂Cl₃N₃O₂, [M+H]⁺).

N-(1,2,3,3-Tetrachloroallylidene)-N^ꢀ-(4-nitrophenyl)-

hydrazine (8) and N-(1,2,3,3-tetrachloroallylidene)-N^ꢀ-(4-

cyanophenyl)hydrazine (9) were synthesized according to

the literature [9]. The synthesis of nitrile 9 was optimized:

A mixture of nitrodiene 1 (500 mg, 1.84 mmol) and

4-cyanoaniline (217 mg, 1.84 mmol) in anhydrous THF

(20 mL) was heated at 45 – 50 ^◦C for 6 d. After evaporation

of the solvent in vacuo, 20 mL of water and 2 mL of conc.

HCl were added. The precipitate was ﬁltered off and washed

with water. Column chromatography (petroleum ether/ethyl

acetate 5:1) gave hydrazone 9 as_◦a colorless powder; yield:

489 mg (86 %); m. p. 201 – 203 C. NMR spectra were in

accordance with the literature.

3,4,4-Trichloro-N,N^ꢀ-bis(4-iodophenyl)-2-nitrobuta-1,3-

diene-1,1-diamine (5)

General method 1, applying 4-iodoaniline; yield: 77 %;

m. p. 138 – 140 ^◦C. – IR (KBr): ν = 3365, 3300, 1591, 1549,

1534, 1483, 1415, 1291, 1268, 1246, 1007, 817, 771, 708,

598, 490 cm⁻¹. – ¹H NMR (CDCl₃): δ = 11.30 (broad s,

1 H, NH), 7.53 (d, J = 8.7 Hz, 4 H), 6.79 (d, J = 8.7 Hz, 4 H),

6.50 (broad s, 1 H, NH). – ¹³C NMR (CDCl₃): δ = 151.9

(C-1), 138.4 (CH), 135.5 (CNH), 128.4, 122.6 (CCl=CCl₂),

125.6 (CH), 110.6 (C-NO₂), 91.3 (C-I). – MS: m/z ( %) =

635 (6) [M]⁺, 599 (33) [M–HCl]⁺, 565 (40) [M–2Cl]⁺, 446

(52), 109 (100). – HRMS ((+)-ESI): m/z = 635.8002 (calcd.

635.8006 for C₁₆H₁₁Cl₃I₂N₃O₂, [M+H]⁺).

N-(1-Amino-2,3,3-trichloroallylidene)-N^ꢀ_◦-(aryl)hydrazines

(10 – 13) were synthesized in MeOH at 0 C, then r. t. from

hydrazines 8 and 9, respectively, according to a previously

published method [9].

N-(2,3,3-Trichloro-1-thiomorpholinoallylidene)-N^ꢀ-(4-nitro-

phenyl)hydrazine (10)

3,4,4-Trichloro-2-nitro-N,N^ꢀ-di-p-tolylbuta-1,3-diene-1,1-

diamine (6)

Yield: 73 %; m. p. 84 – 85 ^◦C. – IR (KBr): ν = 3299,

General method 1, starting from p-toluidine; yield: 82 %; 2919, 1599, 1500, 1414, 1317, 1302, 1273, 1175, 1110, 953,

m. p. 162 – 164 ^◦C. – IR (KBr): ν = 3194, 3027, 2925, 920, 850, 751, 691, 493 cm⁻¹. – ¹H NMR (CDCl₃): δ =

1665, 1631, 1577, 1514, 1417, 1376, 1321, 1116, 963, 858, 8.11 (d, J = 9.2 Hz, 2 H), 7.17 (broad s, 1 H, NH), 6.93

812, 698, 596, 541, 500 cm⁻¹. – ¹H NMR ([D₆]DMSO): (d, J = 9.2 Hz, 2 H), 3.60 – 3.74 (m, 4 H, NCH₂), 2.66 –

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851

2.79 (m, 4 H, SCH₂). – ¹³C NMR (CDCl₃): δ = 150.4 N-(2,3,3-Trichloro-1-(4-methoxyphenylamino)allylidene)-

(C=N), 144.7 (CNH), 139.2 (CNO₂), 126.7 (CCl), 126.2 N^ꢀ-(4-cyanophenyl)hydrazine (13)

(2 C, C_aryl-3,5), 117.9 (CCl₂), 111.2 (2 C, C_aryl-2,6), 48.5

A solution of p-anisidine (0.42 g, 3.4_◦1 mmol) in MeOH

(2 C, NCH₂), 26.5 (2 C, SCH₂). – MS: m/z ( %) = 394 (45)

[M]⁺, 359 (8) [M–Cl]⁺, 324 (4) [M–2Cl]⁺, 285 (10), 102

(100). – HRMS ((+)-ESI): m/z = 394.9890 (calcd. 394.9903

for C₁₃H₁₄Cl₃N₄O₂S, [M+H]⁺).

(10 mL) was added with stirring at 20 C to a suspension

of hydrazone 9 (500 mg, 1.62 mmol) in MeOH (15 mL).

The resulting reaction mixture was stirred for 6 h at 45 –

50 ^◦C. Subsequently, the supernatant liquid was concentrated

in vacuo to a volume of about 5 mL, cooled down to 10 ^◦C,

and then treated with 5 % aqueous HCl (40 mL). After 20 min

stirring, the precipitate was ﬁltered off, washed with water

(2 × 20 mL), and then dried under reduced pressure to give

564 mg (88 %_◦) of hydrazine 13 as a 3 : 1 mixture of isomers.

M. p. 70 – 72 C. – IR (KBr): ν = 3287, 2215 (CN), 1603,

1510, 1312, 1244, 1168, 1034, 886, 829, 547 cm⁻¹. – ¹H

NMR (CDCl₃) (major isomer): δ = 9.88 (broad s, 1 H, NH),

8.52 (broad s, 1 H, NH), 7.58 (d, J = 8.8 Hz, 2 H), 7.12 (d,

J = 8.8 Hz, 2 H), 6.84 – 6.93 (m, 4 H), 3.73 (s, 3 H, OMe). –

¹H NMR (CDCl₃) (minor isomer): δ = 9.42 (broad s, 0.33 H,

NH), 8.90 (broad s, 0.33 H, NH), 7.54 (d, J = 8.8 Hz, 0.66 H),

7.09 (d, J = 8.8 Hz, 0.66 H), 7.03 (d, J = 8.8 Hz, 0.66 H),

6.84 – 6.93 (m, 0.66 H), 3.72 (s, 1 H, OMe). – ¹³C NMR

(CDCl₃) (major isomer): δ = 155.5 (COMe), 149.1 (CNH),

136.6 (C=N), 133.7 (2 C, CH), 133.2 (CNH), 125.5, 123.9

(2 C, CCl=CCl₂), 121.4 (2 C, CH), 120.3 (C≡N), 114.6 (2 C,

CH), 112.6 (2 C, CH), 99.4 (CCN). – ¹³C NMR (CDCl₃)

(minor isomer): δ = 154.1 (COMe), 149.9 (CNH), 139.7

(C=N), 134.5 (CNH), 133.5 (2 C, CH), 125.6, 120.7 (2 C,

CCl=CCl₂), 120.1 (C≡N), 119.4 (2 C, CH), 114.2 (2 C, CH),

111.8 (2 C, CH), 97.5 (CCN). – MS: m/z ( %) = 394 (25)

[M]⁺, 359 (6) [M–Cl]⁺, 324 (8) [M–2Cl]⁺, 264 (16), 123

(100). – HRMS ((+)-ESI): m/z = 395.0229 (calcd. 395.0233

for C₁₇H₁₄Cl₃N₄O, [M+H]⁺).

{2,3,3-Trichloro-1-(4-ﬂuorophenylpiperazin-4-yl)allyl-

idene}-N^ꢀ-(4-nitrophenyl)hydrazine (11)

Yield: 75 %; m. p. 75 – 77 ^◦C. – IR (KBr): ν = 3291, 2827,

1735, 1599, 1508, 1473, 1319, 1302, 1231, 1175, 1110,

1

1043, 941, 832, 751, 693, 493 cm⁻¹. – H NMR (CDCl₃):

δ = 8.14 (d, J = 9.0 Hz, 2 H), 7.20 (broad s, 1 H, NH), 6.78 –

7.08 (m, 6 H), 3.37 – 3.60 (m, 4 H, NCH₂), 3.11 – 3.33 (m,

4 H, NCH₂). – ¹³C NMR (CDCl₃): δ = 155.3 (CF, ¹J_C,F

=

242.6 Hz), 150.3 (C=N), 147.2 (CN, ⁴J_C,F= 4.5 Hz), 144.8

(CNH), 139.4 (CNO₂), 126.7 (CCl), 126.1 (2 C, C_aryl-3,5),

3

118.5 (2 CH, J_C,F= 7.4 Hz), 117.7 (CCl₂), 115.5 (2 CH,

²J_C,F= 22.3 Hz), 111.3 (2 C, C_aryl-2,6), 50.2 (2 C, NCH₂),

45.9 (2 C, NCH₂). – MS: m/z ( %) = (22) 471 [M]⁺, 436 (20)

[M–Cl]⁺, 285 (12), 122 (100). – HRMS ((+)-ESI): m/z =

472.0502 (calcd. 472.0510 for C₁₉H₁₈Cl₃FN₅O₂, [M+H]⁺).

N-(2,3,3-Trichloro-1-pyrrolidinoallylidene)-N^ꢀ-(4-cyano-

phenyl)hydrazine (12)

To a suspension of hydrazone 9 (500 mg, 1.62 mmol) in

MeOH (20 mL) was added a solution of pyrrolidine (0.23 g,

3.25 mmol) in MeOH (5 mL) at 0 ^◦C within 10 min with stir-

ring. The resulting reaction mixture then was stirred for 1 h

at 0 ^◦C and for 3 h at r. t. Subsequently, the supernatant liquid

was concentrated in vacuo to a volume of about 5 mL, cooled

◦

to 10 C and then treated with 5 % aqueous HCl (40 mL).

The precipitate was collected. The residual solution was ex-

tracted with ethyl acetate (5 × 50 mL). Subsequently, the

combined organic layers were washed with brine and dried

over anhydrous sodium sulfate. Evaporation of the solvent

(E)-1,3,4,4-Tetrachloro-1-(4-chlorophenylthio)-2-nitrobuta-

1,3-diene (14)

At r. t. 10.00 g (36.86 mmol) of nitrodiene 1 and 5.44 g

in vacuo gave a crude solid that was dissolved in diethyl (37.60 mmol) of 4-chloro-benzenethiol were combined and

ether. Addition of hexane (50 mL) gave the pure product that stirred 3 d without a solvent. The mixture then was diluted

was isolated, washed with cold hexane (5 mL), and ﬁnally with MeOH (20 mL). The precipitate that appeared was ﬁl-

dried under reduced pressure. Yield: 351 mg, 63 %; m. p. tered off, successively washed twice with water (50 mL each

136 – 138 ^◦C. – IR (KBr): ν = 3309, 2971, 2872, 2209 (CN), portion) and cold MeOH (2 × 50 mL), and ﬁnally dried

1595, 1519, 1429, 1406, 1326, 1273, 1166, 947, 898, 824, unde_◦r reduced pressure. Yield 10.91 g (78 %); m. p. 102 –

544 cm⁻¹.– ¹H NMR (CDCl₃): δ = 7.44 (d, J = 8.8 Hz, 103 C. – IR (KBr): ν = 3080, 1605, 1574, 1536 (NO₂),

2 H), 6.92 (d, J = 8.8 Hz, 2 H), 6.71 (broad s, 1 H, NH), 1478, 1393, 1315, 1294, 1195, 1093, 1003, 923, 821, 760,

3.31 – 3.48 (m, 4 H, NCH₂), 1.93 – 2.05 (m, 4 H, CH₂). – ¹³

C

745, 685, 507 cm⁻¹. – ¹H NMR (CDCl₃): δ = 7.43 – 7.55

NMR (CDCl₃): δ = 149.9 (C=N), 146.6 (CNH), 133.4 (2 C, (m, 4 H). – ¹³C NMR (CDCl₃): δ = 156.8 (C-1), 138.5

C_aryl-3,5), 124.7, 120.5, 119.5 (3 C, CCl=CCl₂, C≡N), 112.3 (C-2), 138.3 (C_quat.), 137.2 (2 CH), 130.0 (2 CH), 129.0,

(2 C, C_aryl-2,6), 99.9 (Ph(C-4)), 47.0 (2 C, NCH₂), 25.0 (2 C, 120.9 (2 C, CCl=CCl₂), 126.9 (C_quat.). – MS: m/z ( %) =

CH₂). – MS: m/z ( %) = 342 (68) [M]⁺, 307 (26) [M–Cl]⁺, 379 (5) [M]⁺, 311 (36), 226 (29), 143 (100) [p-ClPhS⁺]. –

272 (25) [M–2Cl]⁺, 116 (100). – HRMS ((+)-ESI): m/z = HRMS ((+)-ESI): m/z = 509.9842 (calcd. 509.9848 for

343.0281 (calcd. 343.0284 for C₁₄H₁₄Cl₃N₄, [M+H]⁺).

C₁₈H₁₅BrCl₂N₇O₂, [M+H]⁺).

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852

V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

General method 2

(OCH₂), 48.8 (NCH₂), 30.6 (Me). – MS: m/z ( %) = 423

(3) [M]⁺, 388 (5) [M–Cl]⁺, 353 (8) [M–Cl]⁺, 286 (30), 143

(E)-3,4,4-Trichloro-1-(4-chlorophenylthio)-1-morpholino-2-

nitrobuta-1,3-diene (15)

(100) [p-ClPhS⁺] (100). – HRMS ((+)-ESI): m/z = 424.0050

(424.0056 calcd. for C₁₅H₁₇Cl₃N₃O₃S, [M+H]⁺).

◦

At 0 C a solution of 0.18 g (2.1 mmol) morpholine in

(E,E)-3-Benzylamino-4,4-dichloro-1-(4-chlorophenyl-

imino)-1-(4-chlorophenylthio)-2-nitro-but-2-ene (18)

3 mL MeOH was dropwise added to a suspension of 0.38 g

(1.0 mmol) sulfane 14 in 10 mL MeOH. The resulting mix-

ture was stirred for 1 h at the same temperature, then kept

at r. t. for 10 h. After cooling to 0 ^◦C the precipitate was ﬁl-

tered off, washed with water (2 × 10 mL) and cold MeOH

(5 mL) and ﬁnally dried under reduced pressure to yield

Following general method 2, starting from nitrodiene 16

and benzylamine. Yield 75 %; m. p. 133 – 135 ^◦C. – IR (KBr):

ν = 3166, 3088, 1615, 1584 (NO₂), 1481, 1452, 1384 (NO₂),

1242, 1201, 1148, 1090, 1011, 982, 883, 825, 770, 733,

589, 503 cm⁻¹. – ¹H NMR (CDCl₃): δ = 11.35 (broad

s, 1 H, NH), 7.35 – 7.47 (m, 7 H), 7.29 (d, J = 8.7 Hz,

2 H), 7.20 (d, J = 8.7 Hz, 2 H), 7.06 (d, J = 8.7 Hz, 2 H),

6.80 (s, 1 H, CHCl₂), 5.04 (s, 2 H, CH₂). – ¹³C NMR

(CDCl₃): δ = 160.5 (C-1), 151.4 (C_quat.), 146.7 (C_quat.),

137.2 (2 CH), 136.3 (C_quat.), 135.2 (C_quat.), 131.2 (C_quat.),

129.5 (4 CH), 129.1 (2 CH), 128.5 (CH), 127.3 (C_quat.),

127.1 (2 CH), 121.0 (2 CH), 119.8 (C-2), 63.3 (C-4), 49.2

(CH₂). – MS: m/z ( %) = (1) 539 [M]⁺, 504 (2) [M–Cl]⁺,

469 (2) [M–2Cl]⁺, 396 (5) [M–p-ClPhS]⁺, 280 (4), 91

(100). – HRMS ((+)-ESI): m/z = 539.9882 (539.9874 calcd.

for C₂₃H₁₈Cl₄N₃O₂S, [M+H]⁺).

◦

344 mg (80 %) of the desired product; m. p. 167 – 169 C. –

IR (KBr): ν = 2965, 2864, 1531 (NO₂), 1463, 1387, 1279

(NO₂), 1201, 1114, 1092, 1010, 890, 821, 762, 702, 646,

490 cm⁻¹. – ¹H NMR (CDCl₃): δ = 7.36 – 7.47 (m, 4 H),

3.30 – 3.70 (m, 8 H, 4 CH₂). – ¹³C NMR (CDCl₃): δ = 164.6

(C-1), 136.3 (C_quat.), 133.8 (2 CH), 130.5 (2 CH), 129.1

(C_quat.), 126.3, 125.7 (2 C, CCl=CCl₂), 120.1 (C-2), 65.4

(OCH₂), 53.3 (NCH₂). – MS: m/z ( %) = 428 (4) [M]⁺,

393 (30) [M–Cl]⁺, 358 (4) [M–2Cl]⁺, 284 (100) [M–p-

ClPhSH]⁺. – HRMS ((+)-ESI): m/z = 428.9404 (428.9401

calcd. for C₁₄H₁₃Cl₄N₂O₃S, [M+H]⁺).

(E)-3,4,4-Trichloro-1-(4-chlorophenylamino)-1-(4-chloro-

phenylthio)-2-nitrobuta-1,3-diene (16)

Benzotriazole derivative 19

The compound was prepared in 72 % yield from nitrobu-

tadiene 1 in THF according to Kaberdin et al. [20].

Following general method 2, starting from_◦sulfane 14 and

4-chloroaniline at r. t. (10 h), then at 30 – 35 C (3 h). Yield

95 %; m. p. 149 – 150 ^◦C. – IR (KBr): ν = 3198, 3080, 1598,

1551 (NO₂), 1479, 1366, 1343 (NO₂), 1255, 1165, 1090,

General method 3

1

1013, 875, 817, 757, 726, 498 cm⁻¹. – H NMR (CDCl₃):

(E)-(1-Benzotriazol-1-yl)-3,4,4-trichloro-1-(4-ﬂuorophenyl-

δ = 11.44 (broad s, 1 H, NH), 7.17 (d, J = 8.6 Hz, 2 H), 7.12

(d, J = 8.6 Hz, 2 H), 6.95 (d, J = 8.6 Hz, 2 H), 6.90 (d, J =

8.6 Hz, 2 H). – ¹³C NMR (CDCl₃): δ = 158.4 (C-1), 135.8

(C_quat.), 135.4 (C_quat.), 134.1 (2 CH), 133.4 (C_quat.), 129.5

(2 CH), 129.1 (2 CH), 128.5, 123.4 (2 C, CCl=CCl₂), 127.0

(2 CH), 126.7 (C_quat.), 121.9 (C-2). – MS: m/z ( %) = 468 (4)

[M]⁺, 433 (4) [M–Cl]⁺, 398 (4) [M–2Cl]⁺, 325 (17) [M–

p-ClPhS]⁺, 111 (100). – HRMS ((+)-ESI): m/z = 468.8908

(468.8906 calcd. for C₁₆H₁₀Cl₅N₂O₂S, [M+H]⁺).

amino)-2-nitrobuta-1,3-diene (20)

◦

At 0 C 0.117 g (1.05 mmol) 4-ﬂuoroaniline was added

to a suspension of 0.437 g (1.0 mmol) bis(benzotriazolyl)

derivative 19 in MeOH (10 mL). Subsequently, the mix-

◦

ture was stirred for 1 h at 0 C and at r. t. for additional

◦

10 h. The cold mixture (10 C) was diluted with cold wa-

ter (50 mL) and conc. HCl (3 mL). The resulting precipitate

was ﬁltered off, washed with water (2 ×10 mL) and cold

diethyl ether (2 × 3 mL). The product was dried under re-

duced pressure to give 369 mg (86 %); m. p. 118 – 119 ^◦C. –

IR (KBr): ν = 3255, 3099, 1621, 1580 (NO₂), 1503, 1461,

1378 (NO₂), 1293, 1193, 1157, 1044, 949, 878, 835, 744,

(E)-4,4-Dichloro-1-(4-chlorophenylthio)-3-methylamino-1-

morpholino-2-nitrobuta-1,3-diene (17)

Following general method 2 with EtOH as solvent, nitro- 654, 496 cm⁻¹. – ¹H NMR (CDCl₃): δ = 11.60 (broad s,

diene 15 and a 33 % solution of methylamine in abs. EtOH. 1 H, NH), 8.05 (d, J = 8.0 Hz, 1 H), 7.58 – 7.29 (m, 3 H),

Yield 64 %; m. p. 134 – 136 ^◦C. – IR (KBr): ν = 3235, 3150, 6.95 – 6.58 (m, 4 H). – ¹³C NMR (CDCl₃): δ = 161.3 (CF,

2959, 1612, 1494, 1475, 1442, 1361 (NO₂), 1327, 1217, ¹J_C,F= 249.8 Hz), 146.5 (C-1), 145.2 (C_quat.), 131.8 (C_quat.),

1148, 1010, 889, 855, 827, 732, 495 cm⁻¹. – ¹H NMR 130.6 (CNH, ⁴J_C,F= 2.9 Hz), 131.3, 120.7 (2 C, CCl=CCl₂),

([D₆]DMSO): δ = 8.25 (broad s, 1 H, NH), 7.41 (d, J = 129.8 (CH), 125.5 (CH), 125.1 (2 CH, ³J_C,F= 8.7 Hz), 120.7

2

8.0 Hz, 2 H), 7.35 (d, J = 8.0 Hz, 2 H), 3.20 – 3.80 (m, (CH), 119.8 (CNO₂), 116.6 (2 CH, J_C,F= 22.8 Hz), 109.7

8 H, 4 CH₂), 2.34 (s, 3 H, Me). – ¹³C NMR (CDCl₃): δ = (CH). – MS: m/z ( %) = 427 (3) [M]⁺, 392 (3) [M–Cl]⁺, 357

160.9 (C-1), 133.2 (C_quat.), 132.1 (C_quat.), 131.0 (2 CH), (5) [M–2Cl]⁺, 256 (30), 95 (100). – HRMS ((+)-ESI): m/z =

129.4 (2 CH), 128.4 (C_quat.), 123.1 (C-4), 106.0 (C-2), 65.5 427.9892 (427.9884 calcd. for C₁₆H₁₀Cl₃FN₅O₂, [M+H]⁺).

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

853

(E)-(1-Benzotriazol-1-yl)-1-(4-bromophenylamino)-3,4,4-

trichloro-2-nitrobuta-1,3-diene (21)

(CH), 125.3 (CH), 122.6 (2 C, CHCNH), 120.5 (CH), 119.3

(CNO₂), 109.9 (CH), 20.7 (Me). – MS: m/z ( %) = 423 (2)

[M]⁺, 388 (2) [M–Cl]⁺, 353 (3) [M–2Cl]⁺, 91 (100). –

HRMS ((+)-ESI): m/z = 424.0124 (424.0135 calcd. for

C₁₇H₁₃Cl₃N₅O₂, [M+H]⁺).

According to general method

3

wi_◦th 19 and 4-

bromoaniline. Yield 74 %; m. p. 117 – 118 C. – IR (KBr):

ν = 3201, 3089, 2849, 1639, 1575 (NO₂), 1486, 1378 (NO₂),

1295, 1173, 1046, 1008, 950, 874, 811, 785, 745, 622,

497 cm⁻¹. – ¹H NMR (CDCl₃): δ = 11.56 (broad s, 1 H,

NH), 8.07 (d, J = 8.0 Hz, 1 H), 7.57 – 7.34 (m, 3 H), 7.21

(d, J = 8.5 Hz, 2 H, CHCBr), 6.67 (d, J = 8.5 Hz, 2 H,

CHCNH). – ¹H NMR ([D₆]acetone): δ = 11.70 (broad s,

1 H, NH), 8.30 – 8.12 (m, 1 H), 7.92 – 7.60 (m, 3 H), 7.47

(broad s, 2 H, CHCBr), 7.14 (broad s, 2 H, CHCNH). –

¹³C NMR (CDCl₃): δ = 145.9 (C-1), 145.3 (C_quat.), 133.8

(CNH), 132.8 (2 C, CHCBr), 131.8 (C_quat.), 129.9 (CH),

129.8, 120.4 (2 C, CCl=CCl₂), 125.6 (CH), 124.3 (2 C,

CHCNH), 121.4 (CBr), 120.9 (CH), 120.2 (CNO₂), 109.6

(CH). – MS: m/z ( %) = 487 (2) [M]⁺, 452 (3) [M–Cl]⁺,

417 (4) [M–2Cl]⁺, 256 (48), 91 (100). – HRMS ((+)-ESI):

m/z = 487.9170 (487.9083 calcd. for C₁₆H₁₀BrCl₃N₅O₂,

[M+H]⁺).

(E)-(1-Benzotriazol-1-yl)-3,4,4-trichloro-1-(4-ethoxyphenyl-

amino)-2-nitrobuta-1,3-diene (24)

Following general method 3, applying 19 and p-

◦

ethoxyaniline. Yield 83 %; m. p. 137 – 139 C. – IR (KBr):

ν = 3069, 2982, 2873, 1627, 1583 (NO₂), 1498, 1466, 1373

(NO₂), 1294, 1252, 1182, 1119, 1047, 947, 872, 821, 786,

748, 584, 540 cm⁻¹. – ¹H NMR (CDCl₃): δ = 11.71 (broad

s, 1 H, NH), 8.03 (d, J = 8.0 Hz, 1 H), 7.58 – 7.24 (m, 3 H),

6.74 (d, J = 9.0 Hz, 2 H, CHCNH), 6.56 (d, J = 9.0 Hz,

2 H, CHCO), 3.83 (q, J = 7.0 Hz, 2 H, OCH₂), 1.29 (t,

J = 7.0 Hz, 3 H, Me). –¹H NMR ([D₆]acetone): δ = 11.66

(broad s, 1 H, NH), 8.01 (d, J = 8.2 Hz, 1 H), 7.80 – 7.67

(m, 1 H), 7.58 – 7.48 (m, 1 H), 7.47 – 7.36 (m, 1 H), 6.94

(d, J = 8.8 Hz, 2 H, CHCNH), 6.62 (d, J = 8.8 Hz, 2 H,

CHCO), 3.82 (q, J = 6.9 Hz, 2 H, OCH₂), 1.19 (t, J = 6.9 Hz,

3 H, Me). – ¹³C NMR (CDCl₃): δ = 158.2 (CO), 146.6 (C1),

145.1 (C_quat.), 131.9 (C_quat.), 131.7, 121.5 (2 C, CCl=CCl₂),

129.6 (CH), 127.0 (CNH), 125.3 (CH), 124.4 (2 C, CHCNH),

120.5 (CH), 119.5 (CNO₂), 115.1 (2 C, CHCO), 109.9 (CH),

63.6 (CH₂), 14.5 (Me). – MS: m/z ( %) = 453 (2) [M]⁺, 417

(4) [M–HCl]⁺, 383 (3) [M–2Cl]⁺, 296 (10), 119 (100) [ben-

zotriazole]. – HRMS ((+)-ESI): m/z = 454.0204 (454.0240

calcd. for C₁₈H₁₅Cl₃N₅O₃, [M+H]⁺). – HRMS ((+)-ESI):

m/z = 476.0063 (476.0060 calcd. for C₁₈H₁₄Cl₃N₅NaO₃,

[M+Na]⁺).

(E)-(1-Benzotriazol-1-yl)-3,4,4-trichloro-1-(4-iodophenyl-

amino)-2-nitrobuta-1,3-diene (22)

Following general method 3, applying 19 and 4-

iodoaniline. Yield 90 %; m. p. 125 – 126 ^◦C. – IR (KBr): ν =

3098, 1621, 1568 (NO₂), 1486, 1377 (NO₂), 1295, 1250,

1152, 1033, 974, 916, 872, 824, 766, 742, 613, 503 cm⁻¹. –

¹H NMR (CDCl₃): δ = 11.54 (broad s, 1 H, NH), 8.08 (d,

J = 7.8 Hz, 1H), 7.56 – 7.30 (m, 3 H), 7.40 (d, J = 8.5 Hz,

2 H, CHCI), 6.50 (d, J = 8.5 Hz, 2 H, CHCNH). – ¹³C NMR

(CDCl₃): δ = 145.8 (C_quat.), 145.3 (C-1), 138.8 (2 C, CHCI),

134.6 (CNH), 131.8 (C_quat.), 130.0 (CH), 130.6, 120.4 (2 C,

CCl=CCl₂), 125.6 (CH), 124.3 (2 C, CHCNH), 120.9 (CH),

118.5 (CNO₂), 109.6 (CH), 92.6 (CI). – MS: m/z ( %) = 535

(2) [M]⁺, 500 (2) [M–Cl]⁺, 465 (3) [M–2Cl]⁺, 408 (12) [M–

I]⁺, 245 (95), 91 (100).

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-1-(4-ﬂuorophenyl-

imino)-3-(2-hydroxyethylamino)-2-nitrobut-2-ene (25)

Following general method 2 with nitrodiene 20 and 2-

◦

aminoethanol. Yield 70 %; m. p. 121 – 123 C. – IR (KBr):

(E)-(1-Benzotriazol-1-yl)-3,4,4-trichloro-2-nitro-1-(4-tolyl-

amino)buta-1,3-diene (23)

ν = 3420 (OH), 2931, 1642, 1616 (NO₂), 1503, 1449, 1378

(NO₂), 1291, 1225, 1067, 1004, 955, 839, 789, 751, 723,

Applying general method 3 with bis(benzotriazolyl) 669, 529 cm⁻¹. – ¹H NMR ([D₆]acetone): δ = 11.04 (broad

derivative 19 and p-toluidine. Yield 88 %; m. p. 148 – s, 1 H, NH), 8.50 (d, J = 8.3 Hz, 1 H), 8.16 (d, J = 8.1 Hz,

149 ^◦C. – IR (KBr): ν = 3254, 3020, 1627, 1580 (NO₂), 1497, 1 H), 7.76 (ddd, J = 8.3, 7.0, 1.2 Hz, 1 H), 7.61 (ddd, J =

1464, 1375 (NO₂), 1295, 1256, 1176, 1048, 950, 874, 815, 8.1, 7.0, 1.2 Hz, 1 H), 7.26 – 7.12 (m, 4 H), 7.02 (d, J =

785, 745, 697, 658, 489 cm⁻¹. – ¹H NMR (CDCl₃): δ = 1.6 Hz, CHCl₂, 1 H), 4.22 – 3.94 (m, 2 H, OCH₂), 3.93 –

11.70 (broad s, 1 H, NH), 8.04 (dd, J = 8.5, 0.6 Hz, 1 H), 3.82 (m, 2 H, NCH₂), 2.90 (broad s, 1 H, OH). – ¹³C NMR

1

7.51 – 7.30 (m, 3 H), 6.87 (d, J = 8.3 Hz, 2 H, CHCMe), ([D₆]acetone): δ = 162.1 (CF, J_C,F= 243.1 Hz), 153.4

4

6.67 (d, J = 8.3 Hz, 2 H, CHCNH), 2.13 (s, 3 H, Me). – (C_quat.), 147.7 (C_quat.), 146.7 (C_quat.), 143.9 (CN, J_C,F

=

¹H NMR ([D₆]acetone): δ = 11.68 (broad s, 1 H, NH), 8.11 3.1 Hz), 132.2 (C_quat.), 130.5 (CH), 126.9 (CH), 123.8 (2 CH,

(d, J = 7.9 Hz, 1 H), 7.80 (d, J = 7.9 Hz, 1 H), 7.70 – 7.57 ³J_C,F= 8.4 Hz), 120.7 (CH), 117.2 (2 CH, ²J_C,F= 23.0 Hz),

(m, 1 H), 7.54 – 7.44 (m, 1 H), 7.02 (broad s, 4 H, H_arom.), 116.3 (CH), 114.4 (CNO₂), 64.9 (CHCl₂), 60.0 (OCH₂),

2.19 (s, 3 H, Me). – ¹³C NMR (CDCl₃): δ = 146.4 (C-1), 48.4 (NCH₂). – MS: m/z ( %) = 452 (7) [M]⁺, 406 (15)

145.1 (C_quat.), 137.9 (CNH), 132.0 (CMe), 131.8 (C_quat.), [M–NO₂]⁺, 389 (30), 224 (100). – HRMS ((+)-ESI): m/z =

131.6, 119.7 (2 C, CCl=CCl₂), 130.1 (2 C, CHCMe), 129.6 453.0648 (453.0645 calcd. for C₁₈H₁₆Cl₂FN₆O₃, [M+H]⁺).

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854

V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-3-cyclopropyl-

amino-1-(4-ﬂuorophenylimino)-2-nitrobut-2-ene (26)

J = 8.1 Hz, 1 H), 7.75 (ddd, J = 8.3, 7.2, 1.0 Hz, 1 H), 7.59

(ddd, J = 8.1, 7.2, 1.0 Hz, 1 H), 7.53 – 7.25 (m, 5 H, Ph), 7.07

(d, J = 9.0 Hz, 2 H), 7.05 (s, 1 H, CHCl₂), 7.03 (d, J = 9.0 Hz,

According to general method 2 with nitrodiene 20 and cy-

clopropylamine. Yield 83 %; m. p. 106 – 107 ^◦C. – IR (KBr):

ν = 3660, 3285, 3066, 2931, 3066, 1632, 1572 (NO₂), 1501,

1450, 1396 (NO₂), 1308, 1253, 1215, 1053, 952, 896, 837,

771, 755, 630, 530 cm⁻¹. – ¹H NMR (CDCl₃): δ = 10.66

(broad s, 1 H, NH), 8.47 (d, J = 8.3 Hz, 1 H), 8.14 (d, J =

8.1 Hz, 1 H), 7.67 (ddd, J = 8.3, 7.2, 1.2 Hz, 1 H), 7.53

(ddd, J = 8.1, 7.2, 1.2 Hz, 1 H), 7.14 – 6.97 (m, 4 H), 6.28

(d, J = 1.5 Hz, CHCl₂, 1 H), 3.68 – 3.40 (m, 1 H, CHNH),

1.26 – 0.83 (m, 4 H, CH₂). – ¹³C NMR (CDCl₃): δ = 161.4

(CF, ¹J_C,F= 245.9 Hz), 153.0 (C_quat.), 146.9 (C_quat.), 145.4

2 H), 5.21 (s, 2 H, NCH₂), 4.08 (q, J = 6.9 Hz, 2 H, OCH₂),

1.38 (t, J = 6.9 Hz, 3 H, Me). – ¹³C NMR ([D₆]acetone):

δ = 158.5 (CO), 153.0 (C_quat.), 152.8 (C_quat.), 147.7 (C_quat.),

145.3 (C_quat.), 139.7 (C_quat.), 132.2 (C_quat.), 130.3 (CH),

129.7 (2 CH), 128.9 (CH), 128.2 (2 CH), 126.7 (CH), 123.4

(2 C, CHCN), 120.6 (CH), 116.3 (CH), 115.8 (2 C, CHCO),

115.1 (CNO₂), 64.8 (CHCl₂), 64.2 (CH₂O), 49.8 (CH₂N),

15.1 (Me). – MS: m/z ( %) = 524 (3) [M]⁺, 489 (2) [M–Cl]⁺,

478 (2) [M–NO₂]⁺, 91 (100). – HRMS ((+)-ESI): m/z =

525.1218 (525.1209 calcd. for C₂₅H₂₃Cl₂N₆O₃, [M+H]⁺).

4

(C_quat.), 141.7 (CN, J_C,F= 2.9 Hz), 131.2 (C_quat.), 129.7

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-1-(4-ethoxyphenyl-

imino)-3-(2-hydroxyethylamino)-2-nitro-but-2-ene (29)

(CH), 126.0 (CH), 122.9 (2 CH, ³J_C,F= 8.7 Hz), 120.2 (CH),

2

116.7 (2 CH, J_C,F= 22.8 Hz), 115.1 (CH), 114.1 (CNO₂),

62.8 (CHCl₂), 28.0 (CHNH), 10.4 (CH₂), 10.2 (CH₂). – MS:

m/z ( %) = 448 (2) [M]⁺, 402 (2) [M–NO₂]⁺(2), 365 (10)

[M–CHCl₂]⁺, 95 (100). – HRMS ((+)-ESI): m/z = 449.0687

(449.0696 calcd. for C₁₉H₁₆Cl₂FN₆O₂, [M+H]⁺).

Following general method 2, applying nitrodiene 24 and

◦

2-aminoethanol. Yield 92 %; m. p. 92 – 94 C. – IR (KBr):

ν = 3420 (OH), 2980, 2935, 1640, 1614 (NO₂), 1504, 1448,

1378 (NO₂), 1290, 1246, 1170, 1046, 1004, 954, 837, 788,

751, 723, 568, 529 cm⁻¹. – ¹H NMR (CDCl₃): δ = 11.00

(broad s, 1 H, NH), 8.49 (d, J = 8.3 Hz, 1 H), 8.13 (d,

J = 8.1 Hz, 1 H), 7.66 (ddd, J = 8.3, 7.2, 1.0 Hz, 1 H),

7.52 (ddd, J = 8.1, 7.2, 1.0 Hz, 1 H), 7.02 (d, J = 9.0 Hz,

2 H), 6.90 (d, J = 9.0 Hz, 2 H), 6.25 (d, J = 1.5 Hz, 1 H,

CHCl₂), 4.04 (q, J = 7.0 Hz, 2 H, OCH₂), 4.02 – 3.80 (m, 4 H,

OCH₂CH₂N), 1.94 (broad s, 1 H, OH), 1.43 (t, J = 7.0 Hz,

3 H, Me). – ¹³C NMR [D₆]acetone: δ = 158.4 (CO), 153.0

(C_quat.), 147.6 (C_quat.), 145.4 (C_quat.), 139.7 (C_quat.), 132.2

(C_quat.), 130.3 (CH), 126.7 (CH), 123.3 (2 CH), 120.5 (CH),

116.3 (CH), 115.7 (2 CH), 114.8 (CNO₂), 64.9 (CHCl₂),

64.2 (OCH₂), 59.9 (HOCH₂), 48.2 (NCH₂), 15.0 (Me). –

MS: m/z ( %) = 478 (4) [M]⁺, 432 (2) [M–NO₂]⁺, 256 (10),

119 (100). – HRMS ((+)-ESI): m/z = 479.1003 (479.1001

calcd. for C₂₀H₂₁Cl₂N₆O₄, [M+H]⁺).

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-3-(3-hydroxy-

propylamino)-2-nitro-1-(4-tolylimino)-but-2-ene (27)

Following general method 2, starting from nitrodiene 23

◦

and 3-aminopropan-1-ol. Yield 75 %; m. p. 124 – 125 C. –

IR (KBr): ν = 3520, 3016, 2935, 1642, 1601 (NO₂), 1505,

1488, 1381 (NO₂), 1290, 1221, 1192, 1128, 1074, 1005,

968, 893, 829, 788, 751, 723, 595 cm⁻¹. – ¹H NMR

([D₆]acetone): δ = 11.05 (broad s, 1 H, NH), 8.55 (d, J =

8.3 Hz, 1 H), 8.19 (d, J = 8.1 Hz, 1 H), 7.78 (ddd, J = 8.3, 7.3,

0.9 Hz, 1 H), 7.63 (ddd, J = 8.1, 7.3, 0.9 Hz, 1 H), 7.27 (d, J =

8.1 Hz, CHCMe, 2 H), 7.06 (d, J = 8.1 Hz, CHCN, 2 H), 6.96

(d, J = 1.8 Hz, CHCl₂, 1 H), 4.28 – 3.94 (m, 3 H, OH, OCH₂),

3.80 (t, J = 5.8 Hz, 2 H, CH₂NH), 2.32 (s, 3 H, Me), 2.02 –

1.91 (m, 2 H, CCH₂C). – ¹³C NMR ([D₆]acetone): δ = 153.0

(C_quat.), 147.7 (C1), 146.2 (C_quat.), 144.5 (CN), 136.2 (CMe),

132.2 (C_quat.), 130.5 (2 C, CHCMe), 130.3 (CH), 126.7

(CH), 121.3 (2 C, CHCN), 120.5 (CH), 116.2 (CH), 114.4

(CNO₂), 64.8 (CHCl₂), 60.7 (CH₂OH), 45.4 CH₂NH), 32.2

(CH₂C), 20.9 (Me). – MS: m/z ( %) = 462 (3) [M]⁺, 416 (52)

[M–NO₂]⁺, 256 (85), 157 (100). – HRMS ((+)-ESI): m/z =

463.1047 (463.1052 calcd. for C₂₀H₂₁Cl₂N₆O₃, [M+H]⁺).

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-3-(4-ethoxyphenyl-

amino)-1-(4-ethoxyphenylimino)-2-nitro-but-2-ene (30)

Following general method 2, starting from nitrodiene 24

and p-phenetidine. Yield 74 %; m. p. 137 – 138 ^◦C. – IR

(KBr): ν = 3328, 3054, 2978, 1626, 1604, 1565 (NO₂),

1513, 1475, 1450, 1395, 1293 (NO₂), 1240, 1170, 1086,

1

1048, 937, 826, 787, 752, 710, 694, 512 cm⁻¹. – H NMR

([D₆]acetone): δ = 9.04 (broad s, 1 H, NH), 8.13 (d, J =

8.2 Hz, 1 H), 8.09 (d, J = 8.4 Hz, 1 H), 7.74 (s, 1 H,

CHCl₂), 7.60 (ddd, J = 8.2, 7.0, 1.3 Hz, 1 H), 7.55 (ddd,

(E,E)-1-(Benzotriazol-1-yl)-3-(benzylamino)-4,4-dichloro-

1-(4-ethoxyphenylimino)-2-nitro-but-2-ene (28)

According to general method 2 with ni_◦trodiene 24 and J = 8.4, 7.0, 1.3 Hz, 1 H), 7.17 (d, J = 8.8 Hz, 2 H), 7.06

benzylamine. Yield 80 %; m. p. 131 – 132 C. – IR (KBr): (d, J = 8.8 Hz, 2 H), 6.83 (d, J = 8.5 Hz, 2 H), 6.25 (d,

ν = 3417 (OH), 2976, 1648, 1609 (NO₂), 1501, 1449, 1381 J = 8.5 Hz, 2 H), 4.13 (q, J = 7.0 Hz, 2 H, OCH₂), 4.11

(NO₂), 1289, 1231, 1176, 1106, 1058, 1004, 961, 893, 826, (q, J = 7.0 Hz, 2 H, OCH₂), 3.57 (dq, J = 9.3, 7.0 Hz, 1 H,

786, 750, 699, 507 cm⁻¹. – ¹H NMR ([D₆]acetone): δ = OCH₂), 3.25 (dq, J = 9.3, 7.0 Hz, 1 H, OCH₂), 1.42 (t, J =

10.92 (broad s, 1 H, NH), 8.53 (d, J = 8.3 Hz, 1 H), 8.14 (d, 7.0 Hz, 3 H, Me), 1.11 (t, J = 7.0 Hz, 3 H, Me). – ¹³C NMR

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V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

855

([D₆]acetone): δ = 158.7 (CO), 158.6 (CO), 153.1 (C_quat.), m/z = 515.0806 (515.0801 calcd. for C₂₃H₁₈Cl₂FN₆O₃,

153.0 (C_quat.), 147.4 (C_quat.), 143.1 (C_quat.), 139.0 (C_quat.), [M+H]⁺).

131.6 (C_quat.), 129.9 (CH), 126.3 (CH), 126.0 (2 CH), 123.5

(2 CH), 120.6 (CNO₂), 120.2 (CH), 116.0 (2 CH), 115.8

(2 CH), 114.4 (2 CH), 66.1 (CHCl₂), 64.3 (OCH₂), 63.9

(OCH₂), 15.0 (Me), 14.7 (Me). – MS: m/z ( %) = 554 (1)

[M]⁺, 519 (1) [M–Cl]⁺, 436 (1) [M–benzotriazole]⁺, 119

(100). – HRMS ((+)-ESI): m/z = 555.1319 (555.1314 calcd.

for C₂₆H₂₅Cl₂N₆O₄, [M+H]⁺).

(E,E)-1-(Benzotriazol-1-yl)-1-(4-bromophenylimino)-4,4-

dichloro-3-(4-methoxyphenylami-no)-2-nitro-but-2-ene (33)

According to general method 2, starting from nitrodi-

◦

ene 21 and p-anisidine. Yield 80 %; m. p. 149 – 150 C. –

IR (KBr): ν = 3332, 3013, 1636, 1608, 1573 (NO₂), 1510,

1482, 1405, 1305 (NO₂), 1252, 1172, 1071, 1005, 945, 832,

785, 747, 514 cm⁻¹. – ¹H NMR ([D₆]acetone): δ = 9.18

(broad s, 1 H, NH), 8.16 (d, J = 7.7 Hz, 1 H), 8.07 (d,

J = 7.7 Hz, 1 H), 7.68 (d, J = 8.9 Hz, 2 H), 7.67 (s, 1 H,

CHCl₂), 7.62 (ddd, J = 7.7, 7.2, 1.4 Hz, 1 H), 7.58 (ddd,

J = 7.7, 7.2, 1.4 Hz, 1 H), 7.17 (d, J = 8.9 Hz, 2 H), 6.92

(d, J = 8.4 Hz, 2 H), 6.30 (d, J = 8.4 Hz, 2 H), 3.27 (s,

3 H, OMe). – ¹³C NMR ([D₆]acetone): δ = 159.3 (CO),

153.5 (C_quat.), 150.6 (C_quat.), 147.4 (C_quat.), 145.5 (C_quat.),

137.9 (C_quat.), 133.3 (2 CH, CHCBr), 131.5 (C_quat.), 130.3

(CH), 126.7 (CH), 126.0 (2 CH, CHCNH), 123.7 (2 CH,

CHCN), 121.8 (CNO₂), 120.4 (CH), 119.7 (CBr), 115.6

(CH), 114.1 (2 CH, CHCO), 65.9 (CHCl₂), 55.4 (OMe). –

MS: m/z ( %) = 574 [M]⁺(3), 529 [M–HNO₂]⁺(2), 455

[M–benzotriazole]⁺(2), 197 (58), 119 (100). m/z [M+H]⁺

calcd. for C₂₃H₁₈BrCl₂N₆O₃: 575.0001; found: 574.9999.

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-1-(4-ethoxyphen-

ylimino)-3-(4-methoxyphenyl-amino)-2-nitro-but-2-ene (31)

Applying general method 2 with nitrodiene 24 and p-

◦

anisidine. Yield 68 %; m. p. 123 – 125 C. – IR (KBr): ν =

3314, 3058, 1625, 1605, 1568 (NO₂), 1510, 1450, 1395,

1295 (NO₂), 1242, 1170, 1048, 1005, 943, 832, 787, 753,

1

711, 689 cm⁻¹. – H NMR ([D₆]acetone): δ = 9.05 (broad

s, 1 H, NH), 8.13 (d, J = 7.7 Hz, 1 H), 8.09 (d, J = 7.7 Hz,

1 H), 7.75 (s, 1 H, CHCl₂), 7.59 (ddd, J = 7.7, 7.2, 1.0 Hz,

1 H), 7.55 (ddd, J = 7.7, 7.2, 1.0 Hz, 1 H), 7.17 (d, J =

8.9 Hz, 2 H), 7.06 (d, J = 8.9 Hz, 2 H), 6.84 (d, J =

8.5 Hz, 2 H), 6.26 (d, J = 8.5 Hz, 2 H), 4.18 – 4.05 (m, 2 H,

OCH₂), 3.26 (s, 3 H, OMe), 1.41 (t, J = 7.0 Hz, 3 H, Me). –

¹³C NMR ([D₆]acetone): δ = 159.2 (CO), 158.6 (CO),

153.0 (C_quat.), 152.9 (C_quat.), 147.3 (C_quat.), 143.1 (C_quat.),

138.9 (C_quat.), 131.5 (C_quat.), 129.8 (CH), 126.4 (CH), 126.0

(2 CH), 123.5 (2 CH), 120.7 (CNO₂), 120.1 (CH), 116.0

(2 CH), 115.70 (CH), 113.9 (2 CH), 66.1 (CHCl₂), 64.3

(OCH₂), 55.3 (OMe), 15.0 (Me). – MS: m/z ( %) = 540 (1)

[M]⁺, 504 (1) [M–HCl]⁺, 421 (2) [M–benzotriazole]⁺, 119

(100). – HRMS ((+)-ESI): m/z = 541.1158 (541.1158 calcd.

for C₂₅H₂₃Cl₂N₆O₄, [M+H]⁺).

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-1-(4-iodophenyl-

imino)-3-(4-methoxyphenylamino)-2-nitro-but-2-ene (34)

Following general method 2, applying nitrodiene 22 and

p-anisidine. Yield 86 %; m. p. 140 – 141 ^◦C. – IR (KBr): ν =

3329, 3017, 1637, 1608, 1574 (NO₂), 1510, 1487, 1450,

1402, 1305 (NO₂), 1251, 1069, 1050, 1002, 944, 830, 784,

1

747, 513 cm⁻¹. – H NMR ([D₆]acetone): δ = 9.18 (broad

s, 1 H, NH), 8.16 (d, J = 7.7 Hz, 1 H), 8.06 (d, J = 7.7 Hz,

1 H), 7.87 (d, J = 8.7 Hz, 2 H), 7.67 (s, 1 H, CHCl₂), 7.62

(ddd, J = 7.7, 7.1, 1.2 Hz, 1 H), 7.58 (ddd, J = 7.7, 7.2,

1.2 Hz, 1 H), 7.03 (d, J = 8.7 Hz, 2 H), 6.92 (d, J = 8.4 Hz,

2 H), 6.29 (d, J = 8.4 Hz, 2 H), 3.27 (s, 3 H, OMe). – ¹³C

NMR ([D₆]acetone): δ = 159.3 (CO), 153.5 (C_quat.), 147.4

(C_quat.), 146.1 (C_quat.), 145.1 (C_quat.), 139.3 (2 CH, CHCI),

139.1 (C_quat.), 131.5 (C_quat.), 130.3 (CH), 126.7 (CH), 125.9

(2 CH, CHCNH), 123.9 (2 CH, CHCN), 123.6 (CNO₂),

120.3 (CH), 115.5 (CH), 114.1 (2 CH, CHCO), 90.7 (CI),

65.8 (CHCl₂), 55.4 (OMe). – MS: m/z ( %) = 622 [M]⁺

(1), 504 [M–benzotriazole]⁺(2), 476 (6), 373 (10), 91 (100).

m/z [M+H]⁺calcd. for C₂₃H₁₈Cl₂IN₆O₃: 622.9862; found:

622.9863.

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-1-(4-ﬂuorophen-

ylimino)-3-(4-methoxyphenylamino)-2-nitro-but-2-ene (32)

Following general method 2, applying nitrodiene 20 and

p-anisidine. Yield 94 %; m. p. 153 – 154 ^◦C. – IR (KBr):

ν = 3365, 3040, 1634, 1608, 1575, 1511, 1450, 1401, 1322,

1

1254, 1204, 1076, 1052, 1027, 833, 748 cm⁻¹. – H NMR

([D₆]acetone): δ = 9.16 (broad s, 1 H, NH), 8.16 (d, J =

7.9 Hz, 1 H), 8.08 (d, J = 7.9 Hz, 1 H), 7.69 (s, 1 H, CHCl₂),

7.62 (ddd, J = 7.9, 7.2, 1.2 Hz, 1 H), 7.57 (ddd, J = 7.9,

7.2, 1.2 Hz, 1 H), 7.32 – 7.24 (m, 4 H), 6.90 (d, J = 8.5 Hz,

2 H), 6.29 (d, J = 8.5 Hz, 2 H), 3.27 (s, 3 H, OMe). –

¹³C NMR ([D₆]acetone): δ = 162.2 (CF, ¹J_C,F= 250.3 Hz),

159.3 (C_quat.), 153.5 (C_quat.), 147.4 (C_quat.), 144.8 (C_quat.),

4

142.5 (CN, J_C,F= 2.2 Hz), 138.4 (C_quat.), 131.5 (C_quat.),

130.2 (CH), 126.6 (CH), 126.0 (2 CH), 123.8 (CNO₂), 123.6

(E,E)-1-(Benzotriazol-1-yl)-4,4-dichloro-3-(4-methoxy-

phenylamino)-2-nitro-1-(4-tolylimino)-but-2-ene (35)

3

2

(2 CH, J_C,F= 8.5 Hz), 120.3 (CH), 116.9 (2 CH, J_C,F

=

22.8 Hz), 115.6 (CH), 114.1 (2 CH), 65.9 (CHCl₂), 55.4

(Me). – MS: m/z ( %) = 514 (3) [M]⁺, 479 (2) [M–Cl]⁺,

Following the general method 2, applying nitrodiene 23

396 (3) [M–benzotriazole]⁺, 119 (100). – HRMS ((+)-ESI): and p-anisidine. Yield 68 %; m. p. 144 – 145 ^◦C. – IR (KBr):

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ν = 3185, 2926, 1638, 1608, 1569 (NO₂), 1509, 1481, 1394, with stirring at r. t., the precipitate was ﬁltered off, washed

1295 (NO₂), 1246, 1092, 1049, 941, 822, 757, 711 cm⁻¹. – with H₂O (2 × 20 mL), Et₂O (2 × 5 mL), and dried in vacuo

¹H NMR ([D₆]acetone): δ = 9.05 (broad s, 1 H, NH), 8.14 to give acetimidamide 37; yield: 398 mg (78 %); m. p. 135 –

(d, J = 7.9 Hz, 1 H), 8.08 (d, J = 7.9 Hz, 1 H), 7.69 (s, 1 H, 136 ^◦C. – IR (KBr): ν = 3029, 2974, 2856, 1680, 1618, 1570

CHCl₂), 7.60 (ddd, J = 7.9, 7.0, 1.3 Hz, 1 H), 7.56 (ddd, J = (NO₂), 1487, 1296 (NO₂), 1282, 1204, 1071, 1008, 945, 898,

7.9, 7.0, 1.3 Hz, 1 H), 7.32 (d, J = 8.4 Hz, 2 H), 7.10 (d, 826, 746, 498 cm⁻¹. – ¹H NMR ([D₆]acetone): δ = 8.11 (d,

J = 8.4 Hz, 2 H), 6.88 (d, J = 8.7 Hz, 2 H), 6.28 (d, J = J = 8.3 Hz, 1 H), 7.91 (d, J = 8.3 Hz, 1 H), 7.68 (d, J = 8.8 Hz,

8.7 Hz, 2 H), 3.27 (s, 3 H, OMe), 2.39 (s, 3 H). – ¹³C NMR 2 H), 7.63 – 7.56 (m, 1 H), 7.48 (s, 1 H, CHCl₂), 7.46 – 7.41

([D₆]acetone): δ = 159.3 (CO), 153.3 (C_quat.), 147.3 (C_quat.), (m, 1 H), 7.30 (d, J = 8.8 Hz, 2 H), 7.00 (broad s, 2 H, NH₂),

144.0 (C_quat.), 143.7 (C_quat.), 136.6 (C_quat.), 131.5 (C_quat.), 2.52 (s, 3 H, Me). – ¹³C NMR ([D₆]acetone): δ = 170.9

130.7 (2 CH, CHCMe), 130.5 (C_quat.), 130.0 (CH), 126.5 (CMe), 159.8 (C_quat.), 154.1 (C_quat.), 145.0 (C_quat.), 137.6

(CH), 126.0 (2 CH, CHCNH), 121.6 (2 CH, CHCN), 120.6 (C_quat.), 133.2 (2 CH, CHCBr), 131.5 (C_quat.), 131.0 (CH),

(CNO₂), 120.2 (CH), 115.7 (CH), 114.0 (2 CH, CHCO), 66.0 126.7 (CH), 126.6 (2 CH, CHCN), 123.4 (CNO₂), 121.3

(CHCl₂), 55.3 (OMe), 21.0 (Me). – MS: m/z ( %) = 510 (2) (CH), 118.8 (CBr), 116.2 (CH), 68.1 (CHCl₂), 26.2 (Me). –

[M]⁺, 464 (2) [M–NO₂]⁺, 364 (10), 91 (100). – HRMS ((+)- MS: m/z ( %) = 509 (1) [M]⁺, 391 (7) [M–benzotriazole]⁺,

ESI): m/z = 511.1051 (511.1052 calcd. for C₂₄H₂₁Cl₂N₆O₃, 324 (55), 256 (100). – HRMS ((+)-ESI): m/z = 509.9842

[M+H]⁺).

(509.9848 calcd. for C₁₈H₁₅BrCl₂N₇O₂, [M+H]⁺).

4-(4-Bromophenylamino)-6-dichloromethyl-2-methyl-5-

5-(4-Ethoxyphenylamino)-3-(hydrazonomethyl)-4-nitro-1H-

nitro-pyrimidine (38)

pyrazole (36)

To a solution of 37 (0.51 g, 1.0 mmol) in anhydrous THF

(10 mL) at 0 ^◦C sodium hydride (44 mg, 1.1 mmol, 60 % in

mineral oil) was added over 3 min. The mixture was stirred at

0 ^◦C for 1 h and at r. t. for 10 h, then the solvent was removed

at r. t. in vacuo. The residue was treated with aqueous 5 %

HCl (30 mL). After 20 min with stirring at r. t., the precipitate

was ﬁltered off, washed with H₂O (2 × 20 mL), cold MeOH

(1 × 3 mL), hexane (2 × 5 mL) and dried in vacuo to give

To a solution of 7, 28, or 30 (1.0 mmol) in MeOH (10 mL)

at 0 ^◦C a solution of hydrazine hydrate (0.25 g, 5.0 mmol) in

MeOH (2 mL) was added over 2 min. The resulting mix-

◦

ture then was stirred for 1 h at 0 C, then at r. t. for ad-

ditional 4 h in case of 28 and 30 (8 h in case of 7). The

resulting precipitate was ﬁltered off, washed with MeOH

(2 × 5 mL), and ﬁnally dried under reduced pressure to give

83 % of compound 36 by using 28, o_◦r 54 % by using 30,

or 56 % in case of 7. m. p. 201 – 202 C. – IR (KBr): ν =

3423, 3300, 3222, 2971, 2868, 1603, 1572, 1513 (NO₂),

1447, 1369 (NO₂), 1284, 1258, 1233, 1120, 1052, 925, 892,

823, 767, 682, 571 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ =

13.22 (broad s, 1 H, NH), 8.47 (broad s, 1 H, NH), 8.13

(broad s, 2 H, NH₂), 8.07 (s, 1 H, CH=N), 7.61 (d, J =

9.0 Hz, 2 H, CHCNH), 6.86 (d, J = 9.0 Hz, 2 H, CHCO),

3.97 (q, J = 6.9 Hz, 2 H, OCH₂), 1.30 (t, J = 6.9 Hz, 3 H,

Me). – ¹³C NMR ([D₆]DMSO): δ = 153.4 (CO), 147.7 (C-5),

138.7 (C-3), 133.8 (CNH), 122.9 (CH=N), 119.6 (2 CH,

CHCNH), 117.3 (CNO₂), 114.7 (2 CH, CHCO), 63.3 (CH₂),

14.9 (Me). – MS: m/z ( %) = 290 (100) [M]⁺, 261 (51)

[M–C₂H₅]⁺. – HRMS ((+)-ESI): m/z = 291.1203 (291.1206

calcd. for C₁₂H₁₅N₆O₃, [M+H]⁺).

◦

pyrimidine 38; yield: 294 mg (75 %); m. p. 165 – 166 C. –

IR (KBr): ν = 3321, 2924, 2854, 1610, 1567 (NO₂), 1509,

1377 (NO₂), 1284, 1202, 1076, 999, 856, 829, 785, 748, 734,

694, 507 cm⁻¹. – ¹H NMR (CDCl₃): δ = 9.73 (broad s, 1 H,

NH), 7.54 (d, J = 9.0 Hz, 2 H, CHCBr), 7.49 (d, J = 9.0 Hz,

2 H, CHCNH), 7.37 (s, 1 H, CHCl₂), 2.69 (s, 3 H, Me). –

¹³C NMR (CDCl₃): δ = 171.3 (C-2), 160.6 (C_quat.), 153.0

(C_quat.), 135.4 (CNH), 132.2 (2 C, CHCBr), 124.5 (2 C,

CHCNH), 123.5 (CNO₂), 119.1 (CBr), 66.5 (CHCl₂), 26.5

(Me). – MS: m/z ( %) = 390 (100) [M]⁺, 355 (70) [M–Cl]⁺,

344 (3) [M–NO₂]⁺. – HRMS ((+)-ESI): m/z = 390.9362

(390.9364 calcd. for C₁₂H₁₀BrCl₂N₄O₂, [M+H]⁺).

General method 4 (one-pot procedure)

4-(4-Bromophenylamino)-6-dichloromethyl-2-methyl-5-

nitro-pyrimidine (38)

(E,E,E)-4-(Benzotriazol-1-yl)-4-((4-bromophenyl)imino)-

1,1-dichloro-3-nitrobut-2-en-2-yl)acetimidamide (37)

To a suspension of 21 (0.49 g, 1.0 mmol) and acetamidine

To a suspension of 21 (0.49 g, 1.0 mmol) and acetamidine hydrochloride (0.28 g, 3.0 mmol) in anhydrous THF (10 mL)

hydrochloride (0.19 g, 2.0 mmol) in anhydrous THF (10 mL) sodium hydride (0.16 g, 4.0 mmol, 60 % in mineral oil) was

was added sodium hydride (0.12 g, 3.0 mmol, 60 % in min- added at 0 ^◦C over 3 min. Subsequently, after stirring for 1 h

◦

eral oil) at 0 C within 3 min. The resulting mixture was at 0 ^◦C and for 15 h at r. t, the solvent was removed in vacuo at

stirred at 0 ^◦C for 3 h. Subsequently, at the same temperature, r. t. The residue was treated with aqueous 5 % HCl (30 mL).

the solvent was removed in vacuo. The residue was treated After additional 20 min stirring at r. t., the precipitate was

with cold diluted aqueous 5 % HCl (30 mL). After 20 min ﬁltered off, washed with H₂O (2 × 20 mL), cold MeOH (1 ×

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857

3 mL), and hexane (2 × 5 mL), and was then dried in vacuo 6-(Dichloromethyl)-4-(4-ethoxyphenylamino)-2-methyl-5-

to give pyrimidine 38; yield: 235 mg (60 %). Physical data, nitropyrimidine (42)

see above.

Following the general method 4, applying nitrodiene 24.

Yield 47 %; m. p. 168 – 169 ^◦C. – IR (KBr): ν = 3319, 2973,

6-(Dichloromethyl)-4-(4-ﬂuorophenylamino)-2-methyl-5-

nitro-pyrimidine (39)

1610, 1579 (NO₂), 1568, 1512, 1378 (NO₂), 1287, 1253,

1208, 1039, 1001, 858, 824, 785, 748, 672, 570, 510 cm⁻¹. –

¹H NMR ([D₆]DMSO): δ = 9.80 (broad s, 1 H, NH), 7.47

(s, 1 H, CHCl₂), 7.42 (d, J = 8.2 Hz, 2 H, CHCNH), 6.93

(d, J = 8.2 Hz, 2 H, CHCO), 4.02 (q, J = 6.5 Hz, 2 H,

OCH₂), 2.46 (s, 3 H, Me), 1.33 (t, J = 6.5 Hz, 3 H, Me). –

¹³C NMR (CDCl₃): δ = 169.3 (C-2), 156.9 (C_quat.), 156.4

(C_quat.), 152.9 (CO), 130.0 (CNH), 125.8 (2 C, CHCNH),

125.0 (CNO₂), 114.4 (2 C, CHCO), 67.6 (CHCl₂), 63.4

(OCH₂), 26.2 (N₂C-Me), 14.9 (Me). – ¹⁴N and ¹⁵N NMR

(CDCl₃): δ = −13.5 (NO₂), −123.7 (N-1), −129.2 (N-3),

−270.8 (NH). – MS: m/z ( %) = 356 (100) [M]⁺, 327 (20)

[M–C₂H₅]⁺, 322 (32) [M–HCl]⁺. – HRMS ((+)-ESI): m/z =

357.0522 (357.0521 calcd. for C₁₄H₁₅Cl₂N₄O₃, [M+H]⁺).

Following the general method 4 with nitrodiene 20. Yield

62 %; m. p. 152 – 153 ^◦C. – IR (KBr): ν = 3324, 2924, 1617,

1589, 1569 (NO₂), 1511, 1385 (NO₂), 1287, 1202, 1004,

847, 783, 747, 667, 507 cm⁻¹. – ¹H NMR (CDCl₃): δ =

9.71 (broad s, 1 H, NH), 7.53 (dd, J = 8.9, 4.7 Hz, 2 H,

CHCNH), 7.39 (s, 1 H, CHCl₂), 7.12 (dd, J = 8.9, 8.5 Hz,

2 H, CHCF), 2.66 (s, 3 H, Me). – ¹³C NMR (CDCl₃): δ =

1

171.3 (C-2), 160.6 (C_quat.), 160.5 (CF, J_C,F= 246.5 Hz),

4

153.4 (C_quat.), 132.2 (CNH, J_C,F= 3.1 Hz), 125.1 (2 C,

CHCNH, ³J_C,F= 8.2 Hz), 123.3 (CNO₂), 115.9 (2 C, CHCF,

²J_C,F= 22.8 Hz), 66.6 (CHCl₂), 26.5 (Me). – MS: m/z

( %) = 330 (100) [M]⁺, 313 (5) [M–OH]⁺(5), 296 (46)

[M–Cl+H]⁺, 284 (5) [M–NO₂]⁺. – HRMS ((+)-ESI): m/z =

331.0163 (331.0165 calcd. for C₁₂H₁₀Cl₂FN₄O₂, [M+H]⁺).

General method 5

(E)-2-(2,3,3-Trichloro-1-nitroallylidene)-2,3-dihydro-

benzo[d]oxazole (43)

6-(Dichloromethyl)-4-(4-iodophenylamino)-2-methyl-5-

nitro-pyrimidine (40)

At −40 ^◦C a solution of 1 (2.71 g, 10 mmol) in

5 mL MeOH was added dropwise to a suspension of o-

aminophenol (3.49 g, 32 mmol) in 30 mL MeOH within

5 min. The resulting mixture was kept for 1 h at this tem-

perature, and was then allowed to warm to r. t. After 5_◦h stir-

ring, the mixture was poured into a cold solution (0 C) of

5 mL conc. hydrochloric in 250 mL of water. After 20 min,

the precipitate was ﬁltered off, washed with cold water (3 ×

40 mL) and diethyl ether (2 × 10 mL). Drying in vacuo

Following general method 4, applying nitrodiene 22.

Yield 48 %; m. p. 161 – 162 ^◦C. – IR (KBr): ν = 3322, 1613,

1568 (NO₂), 1513, 1379 (NO₂), 1285, 1204, 1002, 855, 826,

785, 749, 508 cm⁻¹. – H NMR (CDCl₃): δ = 9.71 (broad

1

s, 1 H, NH), 7.73 (d, J = 8.8 Hz, 2 H, CHCI), 7.38 (d, J =

8.8 Hz, 2 H, CHCNH), 7.37 (s, 1 H, CHCl₂), 2.69 (s, 3 H,

Me). – ¹³C NMR (CDCl₃): δ = 171.3 (C-2), 160.6 (C_quat.),

153.0 (C_quat.), 138.1 (2 C, CHCI), 136.1 (CNH), 124.7

(2 C, CHCNH), 123.5 (CNO₂), 90.0 (CI), 66.5 (CHCl₂),

26.5 (Me). – MS: m/z ( %) = 438 (100) [M]⁺, 404 (57)

[M–Cl+H]⁺, 370 (7). – HRMS ((+)-ESI): m/z = 438.9232

(438.9226 calcd. for C₁₂H₁₀Cl₂IN₄O₂, [M+H]⁺).

◦

gave oxazole 43; yield: 2.70 g (88 %); m. p. 134 – 135 C. –

IR (KBr): ν = 3423, 3106, 1615, 1582 (NO₂), 1473, 1427,

1368 (NO₂), 1296, 1240, 1073, 970, 925, 850, 805, 751, 587,

486, 420 cm⁻¹. – ¹H NMR (CDCl₃): δ = 12.26 (broad s,

1 H, NH), 7.68 (d, J = 7.3 Hz, 1 H), 7.56 (d, J = 7.5 Hz,

1 H), 7.52 – 7.33 (m, 2 H). – ¹³C NMR (CDCl₃): δ = 159.0

(C-2), 146.9 (C-7a), 128.6 (C-3a), 128.4 (CCl), 126.7 (C-6),

125.5 (C-5), 120.1 (CCl₂), 113.4 (C-4), 111.2 (C-7), 107.1

(CNO₂). – UV λ_max(log ε_max) = 222 nm (4.17), 352 nm

(4.25). – MS: m/z ( %) = 306 (1) [M]⁺, 271 (5) [M–Cl]⁺,

260 (48) [M–NO₂]⁺, 225 (100). – HRMS ((+)-ESI): m/z =

306.9444 (306.9444 calcd. for C₁₀H₆Cl₃N₂O₃, [M+H]⁺).

6-(Dichloromethyl)-2-methyl-5-nitro-4-(4-tolylamino)pyr-

imidine (41)

Following general method 4 with nitrodiene 23. Yield

69 %; m. p. 172 – 173 ^◦C. – IR (KBr): ν = 3323, 2926, 1619,

1573 (NO₂), 1513, 1379 (NO₂), 1285, 1202, 1003, 859,

822, 785, 747, 514 cm⁻¹. – ¹H NMR (CDCl₃): δ = 9.72

(broad s, 1 H, NH), 7.45 (d, J = 8.3 Hz, 2 H, CHCNH),

7.39 (s, 1 H, CHCl₂), 7.22 (d, J = 8.3 Hz, 2 H, CHCMe),

2.67 (s, 3 H, Me), 2.38 (s, 3 H, Me). – ¹³C NMR (CDCl₃):

δ = 171.1 (C-2), 160.5 (C_quat.), 153.2 (C_quat.), 136.1 (CNH),

133.7 (CMe), 129.6 (2 C, CHCMe), 123.3 (CNO₂), 123.1

(E)-2-(2,3,3-Trichloro-1-nitroallylidene)-2,3-dihydro-

benzo[d]thiazole (44)

Following the general method 4, applying nitrodiene 1

(2 C, CHCNH), 66.7 (CHCl₂), 26.5 (N₂C-Me), 21.9 (Me). – and o-aminothiophenol as a 1 : 3.2 mixture. Reaction condi-

MS: m/z ( %) = 326 (100) [M]⁺, 309 (8) [M–OH]⁺, 292 (32) tions: 1 h at −40 ^◦C, then 15 h at r. t. Yield 83 %; m. p. 180 –

[M–HCl]⁺. – HRMS ((+)-ESI): m/z = 327.0415 (327.0416 181 C. – UV: λ_max(log ε_max) = 218 nm (4.38), 382 nm

◦

calcd. for C₁₃H₁₃Cl₂N₄O₂, [M+H]⁺).

(4.43). – IR (KBr): ν = 3444, 3151, 3091, 2775, 1606, 1535

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Table 1. Crystal data and numbers pertinent to data collection

(NO₂), 1466, 1413, 1333 (NO₂), 1249, 1078, 1016, 946, 815,

748, 665, 588, 501 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ =

13.45 (broad s, 1 H, NH), 8.03 (d, J = 8.1 Hz, 1 H, H-7),

7.68 (d, J = 8.1 Hz, 1 H, H-4), 7.55 (ddd, J = 8.1, 7.1, 1.0 Hz,

1 H, H-6), 7.40 (ddd, J = 8.1, 7.1, 1.0 Hz, 1 H, H-5). – ¹³C

NMR ([D₆]DMSO): δ = 160.1 (C-2), 140.1 (C-3a), 128.2

(C-5), 127.8 (C-7a), 127.3 (CCl), 124.8 (C-6), 123.2 (C-5),

121.8 (CCl₂), 114.5 (C-4), 113.6 (CNO₂). – MS: m/z ( %) =

322 (100) [M]⁺, 287 (13) [M–Cl]⁺), 276 (21) [M–NO₂],

252 (12) [M–2Cl], 241 (100). – HRMS ((+)-ESI): m/z =

322.9210 (322.9216 calcd. for C₁₀H₆Cl₃N₂O₂S, [M+H]⁺).

and structure reﬁnement parameters for 30.

Formula

M_r

C₂₆H₂₄Cl₂N₆O₄

555.41

Crystal size, mm³

Crystal system

Space group

0.29×0.28×0.27

Monoclinic

P2₁/n (no. 14)

11.521(2)

16.520(2)

14.306(2)

107.10(1)

2602.3(6)

4

˚

a, A

˚

b, A

˚

c, A

β, deg

3

˚

V, A

Z

2-(2,3,3-Trichloro-1-nitroallylidene)-2,3-dihydro-1H-

benzo[d]imidazole (45)

D_calc, g cm⁻³

1.42

µ(MoK_α), mm⁻¹

0.3

1152

F(000), e

According to the general method 4 with nitrodiene 1 and

o-phenylendiamine as a 1 : 2.1 mixture. Reaction conditions:

1 h at −40 ^◦C, then 3 h at r. t. Yield 96 %; m. p. 215 –

217 ^◦C. – UV: λ_max(log ε_max): 208 nm (4.32), 362 nm

(4.33). – IR (KBr): ν = 3307, 3058, 1621, 1576 (NO₂), 1467,

1370 (NO₂), 1303, 1235, 1150, 1073, 974, 930, 844, 804,

747, 709, 586, 484, 425 cm⁻¹. – ¹H NMR ([D₆]acetone):

δ = 12.26 (broad s, 2 H, NH), 7.72 – 7.51 (m, 2 H), 7.44 –

7.30 (m, 2 H). – ¹³C NMR ([D₆]DMSO): δ = 144.6 (C-2),

131.0 (2 C, C-3a, C-7a), 126.7 (CCl), 124.2 (2 CH, C-5,

C-6), 123.9 (CCl₂), 112.6 (2 C, C-4, C-7), 103.4 (CNO₂). –

MS: m/z ( %) = 305 (4) [M]⁺, 270 (20) [M–Cl]⁺, 259 (15)

[M–NO₂]⁺, 223 (73), 102 (100). – HRMS ((+)-ESI): m/z =

305.9604 (305.9604 calcd. for C₁₀H₇Cl₃N₃O₂, [M+H]⁺).

Diffractometer

θ range for data collection, deg

hkl range

Stoe IPDS 2

1.00 – 25.03

13, pm19, 17

20756 / 4584 / 0.0837

3225

Reﬂections collected / independent / R_int

Reﬂections with I ≥ 2σ(I)

Reﬁned parameters

R1 [I ≥ 2σ(I)] / wR2 (all data)

Goodness-of-ﬁt on₋F₃²

439

0.0543 / 0.0974

1.109

0.219 / −0.255

˚

Peak and hole, e A

˚

Table 2. Selected interatomic distances (A), bond angles

(deg), and dihedral angles (deg) in the structure of 30.

O(1)–C(14)

O(1)–C(17)

O(2)–N(5)

O(3)–N(5)

O(4)–C(22)

O(4)–C(25)

N(1)–N(2)

N(1)–C(1)

N(1)–C(9)

1.370(3)

1.438(4)

1.242(3)

1.238(3)

1.364(4)

1.432(4)

1.376(3)

1.413(3)

1.377(3)

N(2)–N(3)

N(3)–C(10)

N(4)–C(1)

N(4)–C(11)

N(5)–C(2)

N(5)–C(3)

N(5)–C(19)

C(4)–C(19)

1.297(3)

1.391(4)

1.273(4)

1.420(3)

1.427(4)

1.345(4)

1.426(4)

1.774(3)

1.784(3)

(1-(1H-Benzoxazol-2-yl)-3,3-dichloro-2-(4-(dimethyl-

amino)pyridinium-1-yl)allylidene)azinate (46)

Following general method 2, applying benzoxazole 43

◦

and DMAP (1 : 2.1). Reaction conditions: 1 h at 0 C and

12 h at r. t. Yield 32 %; m. p. 203 – 204 ^◦C. – IR (KBr):

ν = 3442, 3105, 1645, 1573, 1532, 1452, 1402, 1362,

1302, 1241, 1145, 1057, 914, 854, 817, 780, 744, 671, 627,

555 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ = 8.31 (d, J =

7.7 Hz, 2 H, NCH), 7.62 – 7.49 (m, 2 H), 7.28 – 7.14 (m,

2H), 7.06 (d, J = 7.7 Hz, 2 H, MeNCCH), 3.24 (s, 6 H,

Me). – ¹³C NMR ([D₆]DMSO): δ = 160.8 (C_quat.-NMe),

156.4 (NCO), 149.6 (C_quat.), 142.4 (C_quat.), 142.3 (2 CH,

N_pyCH), 135.7 (N_pyC_quat.), 124.1 (CH), 122.9 (CCl₂), 122.8

(CH), 117.7 (CH), 109.9 (CH), 107.4 (2 CH, CHCNMe),

103.7 (CNO₂), 40.3 (Me). – MS: m/z ( %) = 392 (1) [M]⁺,

224 (4), 144 (20), 121 (100), 119 (27) [benzoxazole]⁺. –

HRMS ((+)-ESI): m/z = 393.0514 (393.0521 calcd. for

C₁₇H₁₅Cl₂N₄O₃, [M+H]⁺).

N(2)–N(1)–C(1)

N(2)–N(1)–C(9)

N(2)–N(3)–C(10)

N(3)–N(2)–N(1)

120.7(2)

110.1(2)

108.8(2)

108.4(2)

C(3)–N(6)–C(19)

C(9)–N(1)–C(1)

C(22)–O(4)–C(25)

Cl(4)–O(1)–Cl(17)

126.2(2)

129.0(2)

118.3(2)

117.7(2)

N(2)–C(1)–N(1)–N(4)

C(23)–C(22)–O(4)–C(25)

166.6(1)

179.9(1)

MeOH. The mixture was then stirred for 1 d at this temper-

ature. Subsequently, after addition of 200 mL of cold wa-

ter, 5 mL conc. hydrochloric acid was added dropwise. After

10 min stirring, the mixture was extracted with chloroform

(3 × 100 mL). The combined organic layers were washed

with brine and dried over anhydrous calcium chloride. The

crude product was puriﬁed by means of column chromatog-

raphy applying at ﬁrst chloroform to eliminate polar side

products. Afterwards, acetone was used as eluent. Evapora-

tion of all solvents gave 2.19 g azinate 47. Yield 54 %; m. p.

128 – 129 ^◦C. – IR (KBr): ν = 3422, 1645, 1576, 1533, 1469,

(1-(1H-Benzothiazol-2-yl)-3,3-dichloro-2-(4-(dimethyl-

amino)pyridinium-1-yl)allylidene)azinate (47)

At r. t. 2.69 g (22 mmol) DMAP were added to a sus- 1405, 1324, 1284, 1210, 1142, 1078, 1018, 946, 824, 791,

pension of 3.24 g (10.0 mmol) benzothiazole 44 in 50 mL 763, 737, 661 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ = 8.46 (d,

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859

J = 7.6 Hz, 2 H, NCH), 8.04 (d, J = 7.8 Hz, 1 H), 7.87 X-Ray structure determination of 30

(d, J = 7.9 Hz, 1 H), 7.53 (m, 1 H), 7.37 (m, 1 H), 7.07

A suitable single crystal of the title compound was se-

lected under a polarization microscope and mounted in a

glass capillary (d = 0.3 mm). The data collection was carried

out with a single-crystal diffractometer (Stoe IPDS II), using

(d, J = 7.6 Hz, 2 H, MeNCCH), 3.25 (s, 6 H, Me). – ¹³C

NMR ([D₆]DMSO): δ = 161.5 (C_quat.NMe), 156.4 (NCS),

147.0 (C_quat.N), 142.6 (2 CH, N⁺CH), 142.4 (C_quat.S), 133.3

(N⁺C_quat.), 127.3 (CH), 124.4 (CCl₂), 124.1 (CH), 122.5

(CH), 112.0 (CH), 107.3 (2 CH, CHCNMe), 104.2 (CNO₂),

40.4 (Me). – MS: m/z ( %) = 408 (1) [M]⁺, 298 (8), 256 (82),

135 (80) [benzothiazole]⁺, 112 (100). – HRMS ((+)-ESI):

m/z = 409.0281 (409.0293 calcd. for C₁₇H₁₅Cl₂N₄O₂S,

[M+H]⁺).

˚

graphite-monochromatized MoK_αradiation (λ = 0.71073 A)

at T = 223(2) K. The structure was solved by Direct Methods

using SHELXS-97 [21] and reﬁned using alternating cycles

of least-squares reﬁnements against F²(SHELXL-97) [22].

All non-H atoms were located in difference Fourier maps and

were reﬁned with anisotropic displacement parameters. The

H positions were determined by a ﬁnal difference Fourier

synthesis. For preparation of the structure drawings the pro-

grams DIAMOND [23] and POV-RAY [24] were used. Crys-

tallographic data for 30 and details of data collection and

structure reﬁnement are given in Table 1, selected bond

lengths and angles in Table 2.

(1-(1H-Benzimidazol-2-yl)-3,3-dichloro-2-(4-(dimethyl-

amino)pyridinium-1-yl)allylidene)azinate (48)

Following general method 2, applying benzimidazole 45

◦

and DMAP (1 : 2.1). Reaction conditions: 1 h at 0 C and

18 h at r. t. Yield 64 %; m. p. 197 – 198 ^◦C. – IR (KBr):

ν = 3430, 3348, 3051, 1643, 1567, 1523, 1453, 1427, 1365,

1270, 1221, 1171, 1142, 1058, 983, 932, 855, 773, 751, 619,

488 cm⁻¹. – ¹H NMR ([D₆]DMSO): δ = 12.12 (broad s,

1 H, NH), 8.32 (d, J = 7.8 Hz, 2 H, NCH), 7.52 – 7.39 (m,

2 H), 7.06 (d, J = 7.8 Hz, 2 H, MeNCCH), 7.05 – 6.91 (m,

CCDC 769507 contains the supplementary crystallo-

graphic data for this paper. These data can be obtained free

of charge from The Cambridge Crystallographic Data Centre

via www.ccdc.cam.ac.uk/data request/cif.

2 H), 3.21 (s, 6 H, Me). – ¹³C NMR ([D₆]DMSO): δ = 156.4 Acknowledgements

(C_quat.NMe), 148.9 (NCS), 142.2 (2 C, C_quat.N, C_quat.NH),

142.1 (2 CH, N⁺CH), 135.0 (N⁺C_quat.), 125.3 (CCl₂), 120.8

(2 CH), 120.6 (2 CH), 107.4 (2 CH, CHCNMe), 106.2

(CNO₂), 40.2 (Me). – MS: m/z ( %) = 391 (1) [M]⁺, 256

(36), 121 (70), 118 (35) [benzimidazole]⁺, 112 (100). –

HRMS ((+)-ESI): m/z = 392.0688 (392.0681 calcd. for

C₁₇H₁₆Cl₂N₅O₂, [M+H]⁺).

Financial support of this work by Bayer CropScience AG,

Monheim (Germany), is gratefully acknowledged. We thank

Dr. G. Dra¨ger, Leibniz Universita¨t, Hannover (Germany),

for extensive HRMS measurements.

[1] a) V. A. Zapol’skii, R. Fischer, J. C. Namyslo, D. E.

Kaufmann, Bioorg. Med. Chem. 2009, 17, 4206 – 4215;

b) E. Nutz, V. A. Zapol’skii, D. E. Kaufmann, Synthe-

sis 2009, 16, 2719 – 2724; c) V. A. Zapol’skii, J. C.

Namyslo, A. E. W. Adam, D. E. Kaufmann, Heterocy-

cles 2004, 63, 1281 – 1298; d) R. V. Kaberdin, V. I.

Potkin, V. A. Zapol’skii, Russ. Chem. Rev. 1997, 66,

827 – 842.

[2] C. Meyer, V. A. Zapol’skii, A. E. W. Adam, D. E. Kauf-

mann, Synthesis 2008, 16, 2575 – 2581.

[3] H. C. Kolb, M. G. Finn, K. B. Sharpless, Angew. Chem.

2001, 113, 2056 – 2075; Angew. Chem. Int. Ed. 2001,

40, 2004 – 2021.

[7] V. A. Zapol’skii, V. I. Potkin, N. I. Nechai, R. V. Kab-

erdin, M. S. Pevzner, Russ. J. Org. Chem. 1997, 33,

1461 – 1467.

[8] Y. A. Ol’dekop, R. V. Kaberdin, V. I. Potkin, I. A. Shin-

gel, J. Org. Chem. USSR (Engl. Transl.) 1979, 15, 39 –

42.

[9] V. A. Zapol’skii, E. Nutz, J. C. Namyslo, A. E. W.

Adam, D. E. Kaufmann, Synthesis 2006, 17, 2927 –

2933.

[10] a) D. L. Rector, S. D. Folz, R. D. Conklin, L. H.

Nowakowski, G. Kaugarts, J. Med. Chem. 1981, 24,

532 – 538; b) P. Nuhn, A. Bu¨ge, P. Harenberg, H. Let-

tau, K. Moschner, M. Rauchmaul, R. Schneider, Phar-

mazie 1993, 48, 340 – 342.

[4] a) A. E. Cook (Ed.) Enamines: Synthesis, Structure,

and Reactions, Marcel Dekker Inc., New York, 1988,

pp. 165 – 699; b) Z. Rappoport (Ed.) The Chemistry of

Enamines, Wiley, New York, 1994.

[11] C. Ibis, M. C. Sayil, N. G. Deniz, Acta Crystallogr.

2006, E62, o800–o801.

[12] a) G. Aydinli, C. Sayil, C. Ibis, Spectroscopy Lett.

2010, 43, 44 – 50; b) C. Ibis, Z. Gokmen, Acta Crys-

tallogr. 2006, E62, o2932–o2933.

[5] J. Barluenga, C. Valde´s, Chem. Commun. 2005, 4891 –

4901.

[6] V. V. Perekalin, E. S. Lipina, V. M. Berestovitskaya,

D. A. Efremov, Nitroalkenes: Conjugated Nitrocom-

pounds, Wiley, New York, 1994.

[13] R. G. Pearson, J. Am. Chem. Soc. 1963, 85, 3533 –

3539.

[14] a) R. R. Manam, S. Teisan, D. J. White, B. Nicholson,

Brought to you by | Universitaetsbibliothek Frankfurt/Main

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Download Date | 1/31/18 1:51 AM

860

V. A. Zapol’skii et al. · Chemistry of Polyhalogenated Nitrobutadienes

J. Grodberg, S. T. Neuteboom, K. S. Lam, D. A. Mosca,

[19] V. I. Potkin, V. A. Zapol’skii, R. V. Kaberdin, Izv. Akad.

Nauk Bel., Ser. Khim. Nauk. 1996, 40, 68 – 71.

G. K. Lloyd, B. C. M. Potts, J. Nat. Prod. 2005, 68,

240 – 243; b) A. Napolitano, E. Camera, M. Picardo,

M. d’Ischia, J. Org. Chem. 2002, 67, 1125 – 1132.

[20] V. A. Zapol’skii, V. I. Potkin, N. I. Nechai, R. V. Kab-

erdin, Russ. J. Org. Chem. 1993, 29, 731 – 734.

[21] G. M. Sheldrick, SHELXS-97, Program for the Solution

of Crystal Structures, University of Go¨ttingen, Go¨ttin-

gen (Germany) 1997. See also: G. M. Sheldrick, Acta

Crystallogr. 1990, A46, 467 – 473.

[22] G. M. Sheldrick, SHELXL-97, Program for the Reﬁne-

ment of Crystal Structures, University of Go¨ttingen,

Go¨ttingen (Germany) 1997. See also: G. M. Sheldrick,

Acta Crystallogr. 2008, A64, 112 – 122.

[23] K. Brandenburg, DIAMOND (version 3.0), Crystal

and Molecular Structure Visualization, Crystal Im-

pact – K. Brandenburg & H. Putz GbR, Bonn (Ger-

diamond/

[24] POV-RAY (version 3.6), Trademark of Persistence

of Vision Raytracer Pty. Ltd., Williamstown, Victoria

[15] a) Z. Dai, Y. Huang, W. Sadee, P. Blower, J. Med.

Chem. 2007, 50, 1896 – 1906; b) P. Blower, J. H.

Chung, J. S. Verducci, S. Lin, J. K. Park, Z. Dai, C. G.

Liu, T. D. Schmittgen, W. C. Reinhold, C. M. Croce,

J. N. Weinstein, W. Sadee, Mol. Cancer Ther. 2008, 7,

1 – 9.

[16] a) I. M. Lagoja, Chem. Biodiv. 2005, 2, 1 – 50; b) V. A.

Zapol’skii, J. C. Namyslo, C. Altug, M. Gjikaj, D. E.

Kaufmann, Synthesis 2008, 2, 304 – 310.

[17] C. Ibis, Z. Goekmen, Phosphorus Sulfur Silicon Relat.

Elem. 1998, 143, 67 – 75.

[18] T. Ehrhardt, A. Reindl, A. Freund, R. M. Schmidt,

U. Sonnewald, N. M. Stitt, W. Lein, F. Boernke,

K. Deist, PCT Int. Appl. WO 2005054283 A2

20050616, 2005.

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Chemistry of polyhalogenated nitrobutadienes, part 9: Acyclic and heterocyclic nitroenamines and nitroimines from 2-nitroperchlorobuta-1,3-diene

DOI: 10.1515/znb-2010-0710

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