CN102516138A - N-aryl t-butyl sulfonamide, synthetic method and application thereof - Google Patents
N-aryl t-butyl sulfonamide, synthetic method and application thereof Download PDFInfo
- Publication number
- CN102516138A CN102516138A CN2011103345715A CN201110334571A CN102516138A CN 102516138 A CN102516138 A CN 102516138A CN 2011103345715 A CN2011103345715 A CN 2011103345715A CN 201110334571 A CN201110334571 A CN 201110334571A CN 102516138 A CN102516138 A CN 102516138A
- Authority
- CN
- China
- Prior art keywords
- tertiary butyl
- sulfinyl amine
- aryl
- butyl sulfinyl
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 0 CC(C(*)C(*)*C(NS(*(C)(C)C)=O)=C(*)C*)*=C Chemical compound CC(C(*)C(*)*C(NS(*(C)(C)C)=O)=C(*)C*)*=C 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to N-aryl t-butyl sulfonamide, a synthetic method and an application thereof. N-aryl t-butyl sulfonamide has the general molecular formula as shown in the invention, wherein the structure of sulfur atom is R structure, S structure or an arbitrary mixture of the two structures; R1 and R5 are H, C1-C6 alkyl, and R1 and R5 can be the same or different; R2, R3 and R4 are H, C1-C6 alkyl, aryl, nitro, hydrocarbon acyl, formyl, carboxyl, alkoxy and halogen, and R2, R3 and R4 can be the same or different; and R1 and R2 or R2 and R3 form naphthalene ring with A ring. The compound is obtained by a coupling reaction between t butyl sulfenamides and aryl halide C-N under the catalysis of palladium. Under the condition of the catalytic reaction, the chiral structure of the raw material t butyl sulfonamide sulfur atom is maintained in the product. Obvious racemization phenomenon is not generated during the reaction process. The compound provided by the invention can be used as a ligand to promote the addition reaction of zinc ethyl and aromatic aldehyde.
Description
Technical field
The invention belongs to the synthetic of organic chemistry, organic synthesis, chipal compounds, more particularly is exactly N-aryl tertiary butyl sulfinyl amine and compound method and application.
Background technology
The R configuration of enantiomer-pure and S configuration tertiary butyl sulfinyl amine extensively are used for synthesis of chiral amine as the chirality assistant agent, also can be converted into chiral ligand and be used for asymmetric catalysis, have extensive and important purposes.Adjacent hydroxyl tertiary butyl sulfinyl amine of chirality N-and chirality N-o-methoxyphenyl tertiary butyl sulfinyl amine, be in the news as chiral ligand be used for the asymmetry catalysis zinc ethyl to the addition reaction of aromatic aldehyde (
J. Org. Chem. 2007,
72, 1373-1378) with the nucleophilic addition (but do not have concrete data, patent documentation CN 1927830A) of trichlorosilane to imines.In addition, tertiary butyl sulfinyl still is a good amino protecting group, gets off with dilute acid hydrolysis easily.More the purposes of (chirality) N-aryl tertiary butyl sulfinyl amine is also among exploitation.
The compound method of N-aryl tertiary butyl sulfinyl amine is also very limited.Ellmann in 1998 and co-worker thereof use down at-78 ℃ that to meet air be that the incendiary metallic lithium is converted into Lithamide in liquefied ammonia; The latter and aniline reaction; And then with 90.2%ee tertiary butyl-sulfinic acid sulfo-tert-butyl ester reaction, through a series of aftertreatments, obtain the N-phenyl tertiary butyl sulfinyl amine of 89.2%ee; Through further recrystallization, obtain enantiomer-pure N-phenyl tertiary butyl sulfinyl amine (
J. Am. Chem. Soc.,
1998, 120,8011-8019).Qin Yong and co-worker thereof adopt similar method; The ORTHO ANISIDINE and tertiary butyl-sulfinic acid sulfo-tert-butyl ester reaction in the Lithamide/liquefied ammonia system that promptly produces in position; Obtain 80%ee o-methoxyphenyl tertiary butyl sulfinyl amine, but this compound is with Iodotrimethylsilane (CH
3SiI), BF
3, AlCl
3Deng all can not successfully removing methyl.Adjacent under the same conditions allyloxy aniline and the reaction of the tertiary butyl-sulfinic acid sulfo-tert-butyl ester obtain adjacent allyloxy phenyl tertiary butyl sulfinyl amine; The latter is at Pd (PPh
3)
4And NaBH
4Have that successfully taking off allyl group obtains 80%ee o-hydroxy-phenyl tertiary butyl sulfinyl amine down, through twice recrystallization obtain 98.8%ee (
J. Org. Chem. 2007,
72, 1373-1378).In addition, patent documentation (CN 1927830A) is also mentioned o-methoxyphenyl tertiary butyl sulfinyl, compound method like the face document category in front of the method, but successfully use CH
3The protection of SiI demethylating.
Summary of the invention
One of the object of the invention provides enantiomer-pure, the enantiomorph enrichment and racemic N-aryl tertiary butyl sulfinyl amine compound.
Two of the object of the invention provides the compound method of N-aryl tertiary butyl sulfinyl amine compound.
Three of the object of the invention provides N-aryl tertiary butyl sulfinyl amine application of compound.
The present invention develops a kind of new C-N coupling method; It is the C-N coupling method of tertiary butyl sulfinyl amine and halogenated aryl hydrocarbon; And adopting the synthetic a series of N-aryl tertiary butyl sulfinyl amine new compounds of this new coupling method, this compounds can promote the addition reaction of zinc ethyl to phenyl aldehyde.
This compounds has following structural formula:
In the formula, sulphur atom be configured as R configuration, S configuration or any mixing of the two; R
1, R
5Be H, C
1～C
6Alkyl, R
1, R
5Can be identical, also can be different; R
2, R
3, R
4Be H, C
1～C
6Alkyl, aryl, nitro, hydrocarbon acyl group, carboxyl,-oxyl, halogen, R
2, R
3, R
4Can be identical, also can be different; R
1And R
2Perhaps R
2And R
3With the common formation of A ring naphthalene nucleus; R
1, R
2, R
3, R
4, R
5The substituting group that has a non-H at least.
This compounds synthetic C-N coupling tertiary butyl sulfinyl amine and halogenated aryl hydrocarbon under palladium catalysis realize that its reaction equation is following:
In the formula, sulphur atom be configured as R configuration, S configuration or any mixing of the two; R
1, R
5Be H, C
1～C
6Alkyl, R
1, R
5Can be identical, also can be different; R
2, R
3, R
4Be H, C
1～C
6Alkyl, aryl, nitro, hydrocarbon acyl group, carboxyl,-oxyl, halogen, R
2, R
3, R
4Can be identical, also can be different; R
1And R
2Perhaps R
2And R
3With the common formation of A ring naphthalene nucleus; R
1, R
2, R
3, R
4, R
5The substituting group that has a non-H at least.
Tertiary butyl sulfinyl amine (in 1 mmol), halogenated aryl hydrocarbon (1～2 mmol), palladium (Pd for example
2(dba)
3) (0.005～0.06 mmol); Monophosphorus ligand (0.01～0.12 mmol) or biphosphine ligand (0.005～0.06 mmol); Alkali (1～3 mmol) places flask or rub oral examination tube; With argon gas or nitrogen replacement 1～5 time, add 1～20 ml toluene and 0.1～0.6 ml de-oxygenised water, once more with argon gas or nitrogen replacement 1～4 time.50～150 ℃ are stirred 2～48 h down.Add shrend and go out, use ETHYLE ACETATE 10 ml * 2 extractions then.Merge organic phase, add the washing of 10ml saturated common salt.Organic layer is used anhydrous sodium sulfate drying, filters, and vacuum concentration obtains weak yellow liquid.Crude product is used silica gel column chromatography separating purification, with sherwood oil and ETHYLE ACETATE mixed solvent gradient elution, obtains N-aryl tertiary butyl sulfinyl amine.
Embodiment
Further set forth the present invention below by embodiment, therefore do not limit the present invention among the described scope of embodiments.
Embodiment 1
Take by weighing (R)-tertiary butyl sulfinyl amine (0.121g, 1.0 mmol) respectively with electronic balance, p-Nitrobromobenzene (0.262g, 1.3 mmol), Pd
2(dba)
3(0.018g, 0.02 mmol),
tBu-XPhos (0.0212 g, 0.05 mmol), NaOH (0.080 g; 2 mmol); And join successively in the rub oral examination tube, cover anti-mouthful soft rubber ball, go up with argon replaces rub oral examination tube 3 times at Schlenk vacuum line (being also referred to as biexhaust pipe vacuum gas divider).Add 6 ml dry toluenes and 0.3 ml deaerated water with syringe again, then, use the argon replaces rub oral examination tube again 3 times.Then, be put into the rub oral examination tube of replacing rare gas element in 90 ℃ of oil bath pans, and under this temperature, stirred 20 hours.Add shrend after the cooling and go out, with ETHYLE ACETATE (10 ml * 3) extractive reaction mixture.Merge organic phase, add the washing of 10ml saturated common salt.Organic layer is used anhydrous sodium sulfate drying, filters, and filtrate decompression concentrates, and obtains faint yellow thick liquid.Crude product is used purification by silica gel column chromatography, with sherwood oil and ETHYLE ACETATE mixed solvent (from 1:0 to 3:1 (volume ratio)) gradient elution, obtains yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.229g, 95%).Mp:132.6-136.2
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 8.11 (d,
J=9.1 Hz, 2H), 7.04 (d,
J=9.1 Hz, 2H), 6.32 (s, 1H), 1.35 (s, 9H).
13C NMR (75 MHz, CD
3OD), δ (ppm): 148.9,141.6,125.2,115.7,57.3,22.1. IR (KBr), n (cm
-1) 3453,3265,2964,1596,1508,1470,1336,1298,1058,869,794,751. [α]
D 21=-44 (c=0.01, ETHYLE ACETATE).
Embodiment 2
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with parachloronitrobenzene (0.204g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.223g, 92%).The various characterization datas of reaction product are also with product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of embodiment 1.
Embodiment 3
(0.258g 1.3mmol) replaces p-Nitrobromobenzene (0.262g, 1.3 mmol), and other experiment condition and working method are with embodiment 1 with parabromoacetophenone.Obtain yellow solid (R)-N-(to acetylphenyl) tertiary butyl sulfinyl amine (0.220g, 92%).Mp:110.5-111.4
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.67 (d,
J=8.6 Hz, 2H), 6.94 (d,
J=8.7 Hz, 2H), 2.43 (s, 3H), 1.30 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 196.6,147.2,130.7,129.9,115.9,56.8,26.1,22.3. IR (KBr), n (cm
-1) 3456,3276,2961,1693,1611,1509,1475,1356,1182,1119,1056,861,840,712. [α]
D 21=-69.6 (c=0.05, ETHYLE ACETATE).
Embodiment 4
(0.261g 1.3mmol) replaces p-Nitrobromobenzene (0.262g, 1.3 mmol), and other experiment condition and working method are with embodiment 1 with parabromobenzoic acid.Obtain white solid (R)-N-(to carboxyl phenyl) tertiary butyl sulfinyl amine (0.161g, 67%). Mp:164.2
oC.
1H NMR (300 MHz, CD
3OD), δ (ppm): 7.94 (d,
J=9.0 Hz, 2H), 7.17 (d,
J=9.0 Hz, 2H), 1.32 (s, 9H).
13C NMR (75 MHz, CD
3OD), δ (ppm): 168.5,147.9,131.5,124.2,116.4,56.9,21.7. IR (KBr), n (cm
-1) 3481,3186,2985,1703,1671,1608,1461,1425,1286,1238,1172,1056,8801,768. [α]
D 21=-63.3 (c=0.078, ETHYLE ACETATE).
Embodiment 5
(0.227g 1.3mmol) replaces p-Nitrobromobenzene (0.262g, 1.3 mmol), and other experiment condition and working method are with embodiment 1 with P-Bromofluorobenzene.Obtain yellow solid (R)-N-(to fluorophenyl) tertiary butyl sulfinyl amine (0.067g, 31%). Mp:59.2
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 6.96 (d,
J=6.4 Hz, 4H), 5.36 (s, 1H), 1.33 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 160.6,138.0,120.5 (d,
J=31.8 Hz, 2C), 115.9 (d,
J=90.3 Hz, 2C), 56.5,22.4. IR (KBr), n (cm
-1) 3448,3227,2963,2926,2612,1607,1506,1473,1367,1336,1273,1209,1157,1135,1100,1069,886,833,776. [α]
D 21=-73.0 (c=0.01, ETHYLE ACETATE).
Embodiment 6
(0.243g 1.3mmol) replaces p-Nitrobromobenzene (0.262g, 1.3 mmol), and other experiment condition and working method are with embodiment 1 with NSC 82293.Obtain yellow solid (R)-N-(m-methoxyphenyl) tertiary butyl sulfinyl amine (0.186g, 82%).Mp:110.9-111.9
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.16 (t,
J=8.2 Hz, 1H), 5.60-5.55 (m, 3H), 5.34 (s, 1H), 3.78 (s, 3H), 1.33 (s, 9H).
13C NMR (75 MHz, CD
3OD), δ (ppm): 160.2,143.5,129.8,110.1,107.9,103.5,56.3,54.9,22.3. IR (KBr), n (cm
-1): 3456,3273,3112,3076,2966,1584,1519,1246,1186,1113,1068,875,795,751. [α]
D 21=-2.6 (c=0.05, ETHYLE ACETATE).
Embodiment 7
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with para-bromo toluene (0.222 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-methylphenyl) tertiary butyl sulfinyl amine (0.188 g, 89%).Mp:81-83
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.06 (d,
J=8.0 Hz, 2H), 6.90 (d,
J=8.1 Hz, 2H), 5.33 (s, 1H), 2.28 (s, 3H), 1.32 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 139.4,132.3,129.7,118.7,56.2,22.4,20.5. IR (KBr), n (cm
-1): 3445,3242,2957,2922,2864,1613,1513,1472,1382,1275,1228,1177,1050,881,810. [α]
D 21=-114.0 (c=0.01, ETHYLE ACETATE).Under identical experiment condition; Through the chirality liquid chromatography of this product and the liquid chromatography of raceme (asking for an interview embodiment 9) contrast; Appearance time is consistent with raceme; Through calculating, the enantiomeric excess value of this product is that 98%ee (R configuration) (annotates: chiral reagent R configuration tertiary butyl sulfinyl amine enantiomeric excess value 98%ee).
Embodiment 8
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with para-bromo toluene (0.222 g, 1.3 mmol); With (S)-tertiary butyl sulfinyl amine (0.121g; 1.0 mmol) replace (R)-tertiary butyl sulfinyl amine (0.121g, 1.0 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-methylphenyl) tertiary butyl sulfinyl amine (0.184 g, 87%).Mp:80-83
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.06 (d,
J=8.0 Hz, 2H), 6.90 (d,
J=8.1 Hz, 2H), 5.33 (s, 1H), 2.28 (s, 3H), 1.32 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 139.4,132.3,129.7,118.7,56.2,22.4,20.5. IR (KBr), n (cm
-1): 3445,3242,2957,2922,2864,1613,1513,1472,1382,1275,1228,1177,1050,881,810. [α]
D 21=+118.2 (c=0.01, ETHYLE ACETATE).Under identical experiment condition; Through the chirality liquid chromatography of this product and the liquid chromatography of raceme (asking for an interview embodiment 9) contrast; Appearance time is consistent with raceme; Through calculating, the enantiomeric excess value of this product is that 98%ee (S configuration) (annotates: chiral reagent S configuration tertiary butyl sulfinyl amine enantiomeric excess value 98%ee).
Embodiment 9
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with para-bromo toluene (0.222 g, 1.3 mmol); With (±)-tertiary butyl sulfinyl amine (0.121g; 1.0 mmol) replace (R)-tertiary butyl sulfinyl amine (0.121g, 1.0 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (±)-N-(p-methylphenyl) tertiary butyl sulfinyl amine (0.178 g, 84%).Mp:80-82
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.06 (d,
J=8.0 Hz, 2H), 6.90 (d,
J=8.1 Hz, 2H), 5.33 (s, 1H), 2.28 (s, 3H), 1.32 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 139.4,132.3,129.7,118.7,56.2,22.4,20.5. IR (KBr), n (cm
-1): 3445,3242,2957,2922,2864; 1613,1513,1472,1382,1275; 1228,1177,1050,881, the chirality liquid-phase chromatographic analysis situation of 810. these racemies: in day island proper Tianjin LC-20AB of instrument company high performance liquid chromatograph (moving phase
V(normal hexane)/
V(Virahol)=90/10, flow velocity are 1.0 ml/min, room temperature, and the SPD-20AB UV-detector, detecting wavelength is 254
Nm) go up and use the Chiralcel OD-H of Daisel chemical industry Co., Ltd chiral column (250x4.6mm; Particle diameter 5mm) (±)-N-(p-methylphenyl) tertiary butyl sulfinyl amine is carried out chiral separation, R configuration and S configuration N-(p-methylphenyl) tertiary butyl sulfinyl amine isomer appearance time are respectively: t
R=4.6 minutes, t
S=7.0 minutes; Two peak area ratios are 1:1, and this this product of proof is a raceme, and reaches baseline separation.
Embodiment 10
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with o-bromotoluene (0.222 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(o-tolyl) tertiary butyl sulfinyl amine (0.129g, 61%).Mp:62-64
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.18-7.11 (m, 3H), 7.00-6.93 (m, 1H), 5.25 (s, 1H), 2.29 (s, 3H), 1.34 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 139.8,130.7,127.5,127.0,123.3,119.1,56.4,22.4,17.6. IR (KBr), n (cm
-1): 3452,3248,2959,1589,1492,1373,1277,1238,1177,1062,871,748. [α]
D 21=-67.3 (c=0.03, ETHYLE ACETATE).
Embodiment 11
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with m-bromotoluene (0.222 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain white solid (R)-N-(tolyl) tertiary butyl sulfinyl amine (0.148g, 70%).Mp:84
oC.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.15 (t,
J=7.9 Hz, 1H), 6.84-6.79 (m, 3H), 5.30 (s, 1H), 2.30 (s, 3H), 1.33 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 142.0,139.1,129.0,123.4,118.8,115.2,56.3,22.4,21.3. IR (KBr), n (cm
-1): 3451,3246,2965,1605,1474,1368,1289,1165,1047,937,874,829,776. [α]
D 21=-127.5 (c=0.06, ETHYLE ACETATE).
Embodiment 12
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with 1-naphthlene bromide (0.266 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain brown oil (R)-N-(1-naphthyl) tertiary butyl sulfinyl amine (0.062g, 25%).
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.96 (s, 1H), 7.83 (t,
J=5.0 Hz, 1H), 7.60 (d,
J=2.2,1H), 7.51-7.48 (m, 2H), 7.36 (t,
J=5.4 Hz, 2H), 5.84 (s, 1H), 1.42 (s, 9H).
13C NMR (75 MHz, CD
3OD), δ (ppm): 136.9,134.2,128.5,127.3,126.1,125.9,125.6,124.6,121.2,117.4,66.9,22.6. IR (KBr), n (cm
-1): 2973,2868,1580,1513,1459,1396,1320,1266,1174,1057,1057,891,771. [α]
D 21=-43.5 (c=0.04, ETHYLE ACETATE).
Embodiment 13
Replace p-Nitrobromobenzene (0.262g, 1.3 mmol) with 2-naphthlene bromide (0.266 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain white solid (R)-N-(2-naphthyl) tertiary butyl sulfinyl amine (0.173 g, 70%). Mp:122-124 ℃.
1H NMR (300 MHz, CDCl
3), δ (ppm): 1.37 (s, 9 H), 6.08 (s, 1 H), 7.15 (d,
J=8.7 Hz, 1H), 7.27-7.39 (m, 3 H), 7.58-7.66 (m, 3 H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 139.7,133.9,129.7,129.1,127.5,126.6,126.4,124.1,119.0,113.5,56.5,22.4. IR (KBr), n (cm
-1): 3454,3202,2961,1628,1599,1511,1464,1386,1364,1340,1247,1210,1177,1067,961,918,850,820,742. [α]
D 21=-134.2 (c=0.1, ETHYLE ACETATE).
Embodiment 14
Use bromo biphenyl (0.301 g, 1.3 mmol) is replaced p-Nitrobromobenzene (0.262g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(to xenyl) tertiary butyl sulfinyl amine (0.224g, 82%).Mp:153-156
oC.
1H NMR (300 MHz, CDCl
3) δ (ppm): 7.49-7.29 (m, 7H), 7.06 (d,
J=8.5 Hz, 2H), 6.03 (d,
J=3.9 Hz, 1H), 1.37 (s, 9H).
13C NMR (75 MHz, CDCl
3) δ (ppm): 141.5,140.4,135.5,128.6,127.8,126.7,126.6,118.3,56.4,22.4. IR (KBr), n (cm
-1) 3453,3252,2926,1610,1519,1485,1386,1305,1286,1268,1228,1191,1057,912,880,838,767. [α]
D 21=-110.8 (c=0.1503, ETHYLE ACETATE).
Embodiment 15
Replace p-Nitrobromobenzene (0.262 g, 1.3 mmol) with m-chloro-nitrobenzene (0.204 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(m-nitro) tertiary butyl sulfinyl amine (0.168 g, 71%).Mp:146-149 ℃.
1H NMR (300 MHz, CDCl
3), δ (ppm): 7.79 (s, 1H), 7.69 (dd,
J 1 =1.68 Hz,
J 2=4.45 Hz, 1H), 7.27 (d,
J=5.2 Hz, 2H), 6.66 (s, 1H), 1.36 (s, 9H).
13C NMR (75 MHz, CDCl
3), δ (ppm): 148.7,143.9,129.9,123.0,116.9,111.9,57.1,22.4. IR (KBr), n (cm
-1): 3453,3076,2965,2861,1619,1527,1476,1401,1349,1293,1238,1055,996,948,884,826,801,737. [α]
D 21=-2.1 (c 0.0243, ETHYLE ACETATE).
Embodiment 16
(0.240g 1.3mmol) replaces p-Nitrobromobenzene (0.262g, 1.3 mmol), and other experiment condition and working method are with embodiment 1 with p-bromobenzaldehyde.Obtain orange/yellow solid (R)-N-(to the formyl radical phenyl) tertiary butyl sulfinyl amine (0.063g, 28%).Mp:?125-127?
oC.?
1H?NMR?(300?MHz,?CDCl
3),?δ?(ppm):?9.78?(s,?1H),?7.66?(d,?
J?=?8.4?Hz,?2H),?7.05?(d,?
J?=?8.5?Hz,?2H),?6.64?(s,?1H),?1.34?(s,?9H).?
13C?NMR?(75?MHz,?CDCl
3),?d?(ppm):?190.6,?139.7,?133.8,?129.7,?111.9,?57.1,?22.4.?IR?(KBr),?n?(cm
-1):?3450,?3212,?2953,?2926,?2828,?2746,?1688,?1602,?1507,?1457,?1388,?1368,?1294,?1235,?1161,?1059,?869,?815,?778.
Embodiment 17
With Pd (dba)
2(0.023g, 0.04 mmol) replaces Pd
2(dba)
3(0.018g, 0.02 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.223g, 92%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 18
Use PdCl
2(0.007g, 0.04 mmol) replaces Pd
2(dba)
3(0.018g, 0.02 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.105g, 43%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 19
With Pd (OAc)
2(0.009g, 0.04 mmol) replaces Pd
2(dba)
3(0.018g, 0.02 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.145g, 60%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 20
Use Pd
2(dba)
3(0.009g, 0.01 mmol) replaces Pd
2(dba)
3(0.018g, 0.02 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.152g, 63%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 21
Use Pd
2(dba)
3(0.005g, 0.005 mmol) replaces Pd
2(dba)
3(0.018g, 0.02 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.110g, 45%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 22
Replace argon gas with nitrogen, other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.216g, 89%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 23
With 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl (0.024g, 0.05 mmol) replaces
tBu-XPhos (0.021 g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.195g, 80%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 24
Replace with 2-di-t-butyl phosphine biphenyl (0.015g, 0.05 mmol)
tBu-XPhos (0.021 g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.225g, 93%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 25
Replace with 2-dicyclohexylphosphontetrafluoroborate biphenyl (0.018 g, 0.05 mmol)
tBu-XPhos (0.021 g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.216 g, 89%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 26
Replace with tri-butyl phosphine (0.010 g, 0.05 mmol)
tBu-XPhos (0.021 g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.186 g, 77%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 27
With 2-dicyclohexyl phosphorus-2', 6'-dimethoxy-biphenyl (0.021g, 0.05 mmol) replaces
tBu-XPhos (0.021g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.169g, 70%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 28
Replace with 2-two hexamethylene phosphino--2'-(N, TMSDMA N dimethylamine)-biphenyl (0.020g, 0.05 mmol)
tBu-XPhos (0.021g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.153g, 63%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 29
With 2,2'-pair-(diphenyl phosphine)-1,1'-dinaphthalene (0.016 g, 0.025 mmol) replaces
tBu-XPhos (0.021 g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.146g, 60%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 30
With 4, the two diphenylphosphines-9 of 5-, 9-dimethyl-oxa-anthracene (0.025 g, 0.025 mmol) replaces
tBu-XPhos (0.021g, 0.05 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.162g, 67%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 31
(0.112g 2mmol) replaces NaOH (0.080 g, 2 mmol), and other experiment condition and working method are with embodiment 1 with Pottasium Hydroxide.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.213g, 88%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 32
Replace NaOH (0.080 g, 2 mmol) with sodium tert-butoxide (0.192 g, 2 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.226g, 93%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 33
Replace NaOH (0.080 g, 2 mmol) with potassium tert.-butoxide (0.224 g, 2 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.203 g, 84%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 34
Replace NaOH (0.080 g, 2 mmol) with a water cesium hydroxide (0.336 g, 2 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.218g, 90%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 35
Temperature of reaction replaces 90 ℃ with 120 ℃, and other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.177 g, 73%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 36
Do not add deaerated water (0.03 ml) in the reaction system, other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine (0.194 g, 80%).Product (R)-N-(p-nitrophenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 1 consistent.
Embodiment 37
Use toluene iodide (0.284 g, 1.3 mmol) is replaced p-Nitrobromobenzene (0.262 g, 1.3 mmol), other experiment condition and working method are with embodiment 1.Obtain yellow solid (R)-N-(p-methylphenyl) tertiary butyl sulfinyl amine (0.067 g, 28%).Product (R)-N-(p-methylphenyl) tertiary butyl sulfinyl amine of the various characterization datas of reaction product and embodiment 7 consistent.
Embodiment 38
In the 50ml round-bottomed flask of band magnetic stirring bar, oven dry, add 5 ml dry toluenes, (202 ml, 2 mmol) phenyl aldehyde, (0.042 g; 0.2 mmol) N-is to toluene tertiary butyl sulfinyl amine; Cover anti-mouthful soft rubber ball, receive on the Schlenk vacuum line, with argon replaces 4 times.Then, place this round-bottomed flask ice-water bath to stir, draw (3 ml, 3 mmol) 1.0 M zinc ethyl hexane solutions with syringe again and be injected in the round-bottomed flask.React after 12 hours and inject 2 ml 2M Hydrogen chloride cancellation reaction through syringe.With 10 ml ethyl acetate extractions 3 times, merge organic phase, use anhydrous magnesium sulfate drying, filter, to filtrate with the Rotary Evaporators concentrating under reduced pressure, crude product passes through silica gel column chromatography separating purification, obtains (0.256 g, 94%) colourless oil liquid 1-phenyl propanol.
Embodiment 39
With (0.045 g, 0.2 mmol) (R)-N-(m-methoxyphenyl) tertiary butyl sulfinyl amine replace (0.042 g, 0.2 mmol) (R)-N-is to toluene tertiary butyl sulfinyl amine, other experiment condition and working method are with embodiment 38.Obtain (0.264 g, 97%) colourless oil liquid 1-phenyl propanol.
Claims (7)
1. N-aryl tertiary butyl sulfinyl amine is characterized in that it is the compound of following structural formula:
In the formula, sulphur atom be configured as R configuration, S configuration or any mixing of the two; R
1, R
5Be H, C
1～C
6Alkyl, R
1, R
5Can be identical, also can be different; R
2, R
3, R
4Be H, C
1～C
6Alkyl, aryl, nitro, hydrocarbon acyl group, formyl radical, carboxyl,-oxyl, halogen, R
2, R
3, R
4Can be identical, also can be different; R
1And R
2Perhaps R
2And R
3With the common formation of A ring naphthalene nucleus; R
1, R
2, R
3, R
4, R
5The substituting group that has a non-H at least.
2. the compound method of N-aryl tertiary butyl sulfinyl amine according to claim 1; Be under argon gas or nitrogen protection; In the presence of palladium, phosphine part and alkali; The C-N cross-coupling reaction takes place and generates N-aryl tertiary butyl sulfinyl amine in tertiary butyl sulfinyl amine and halogenated aryl hydrocarbon, and its synthetic general formula is following:
In the formula, sulphur atom be configured as R configuration, S configuration or any mixing of the two; R
1, R
5Be H, C
1～C
6Alkyl, R
1, R
5Can be identical, also can be different; R
2, R
3, R
4Be H, C
1～C
6Alkyl, aryl, nitro, hydrocarbon acyl group, formyl radical, carboxyl,-oxyl, halogen, R
2, R
3, R
4Can be identical, also can be different; R
1And R
2Perhaps R
2And R
3With the common formation of A ring naphthalene nucleus; R
1, R
2, R
3, R
4, R
5The substituting group that has a non-H at least.
3. the synthetic method of N-aryl tert-butyl group sulfenamide according to claim 2 is characterized in that said palladium is that three (dibenzalacetones), two palladiums (0) (are abbreviated as Pd
2(dba)
2), two (dibenzalacetone) palladium (0) (is abbreviated as Pd (dba)
2), four (triphenylphosphines) close palladium (0), palladium (is abbreviated as Pd (OAc)
2), (molecular formula is PdCl to palladium bichloride
2); Tert-butyl group sulfenamide: halogenated aryl hydrocarbon: the mol ratio of palladium is 1: 0.9～2: 0.005～0.06.
4. the compound method of N-aryl tertiary butyl sulfinyl amine according to claim 2 is characterized in that said phosphine part is 2-di-t-butyl phosphine-2', 4', 6'-tri isopropyl biphenyl (another name
tBu-XPhos), 2-dicyclohexylphosphontetrafluoroborate-2', 4', 6'-tri isopropyl biphenyl (another name XPhos), 2-di-t-butyl phosphine biphenyl (another name JohnPhos), 2-dicyclohexylphosphontetrafluoroborate biphenyl (another name Cy-JohnPhos), tri-butyl phosphine (another name
tBu
3P), 2-dicyclohexyl phosphorus-2', 6'-dimethoxy-biphenyl (another name SPhos), 2-two hexamethylene phosphino--2'-(N, TMSDMA N dimethylamine)-biphenyl (another name
tBu-DavePhos), 2,2'-pair-(diphenyl phosphine)-1,1'-dinaphthalene (another name BINAP), 4, the two diphenylphosphines-9 of 5-, 9-dimethyl-oxa-anthracene (another name XantPhos); The mol ratio of phosphine part and palladium is 1～2: 1 (for monophosphorus ligand), perhaps 0.5～1: 1 (for biphosphine ligand).
5. the compound method of N-aryl tertiary butyl sulfinyl amine according to claim 2 is characterized in that said alkali is sodium hydroxide, Pottasium Hydroxide, cesium hydroxide, sodium tert-butoxide, potassium tert.-butoxide; The mol ratio of alkali and halogenated aryl hydrocarbon is 1～3: 1.
6. the compound method of N-aryl tertiary butyl sulfinyl amine according to claim 2 is characterized in that 20～150 ℃ of temperature of reaction, is preferably 70～110 ℃, and the reaction times is 2～48 hours, is preferably 12～28 hours.
7. N-aryl tertiary butyl sulfinyl amine according to claim 1, its purposes are to promote the addition reaction of zinc ethyl to phenyl aldehyde as part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103345715A CN102516138A (en) | 2011-10-31 | 2011-10-31 | N-aryl t-butyl sulfonamide, synthetic method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103345715A CN102516138A (en) | 2011-10-31 | 2011-10-31 | N-aryl t-butyl sulfonamide, synthetic method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102516138A true CN102516138A (en) | 2012-06-27 |
Family
ID=46287274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103345715A Pending CN102516138A (en) | 2011-10-31 | 2011-10-31 | N-aryl t-butyl sulfonamide, synthetic method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102516138A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725267A (en) * | 2014-04-10 | 2015-06-24 | 申俊 | Method for synthesizing imide compound |
| CN104744290A (en) * | 2014-04-10 | 2015-07-01 | 申俊 | Synthesis method of imide compound |
| CN106187836A (en) * | 2016-07-01 | 2016-12-07 | 成都理工大学 | Chirality N cinnamyl N phenyl t-butyl sulfenamide and preparation and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927830A (en) * | 2006-10-24 | 2007-03-14 | 中国科学院成都生物研究所 | Compound of optically pure sulfenamides and application thereof |
-
2011
- 2011-10-31 CN CN2011103345715A patent/CN102516138A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1927830A (en) * | 2006-10-24 | 2007-03-14 | 中国科学院成都生物研究所 | Compound of optically pure sulfenamides and application thereof |
Non-Patent Citations (5)
| Title |
|---|
| DATTA, MRITYUNJOY等: "N-(3-Methoxyphenyl)-tert-butanesulfinamide", 《ACTA CRYSTALLOGRAPHICA, SECTION E：STRUCTURE REPORTS ONLINE》 * |
| HUANG, ZHIYAN等: "Syntheses of Novel Chiral Sulfinamido Ligands and Their Applications in Diethylzinc Additions to Aldehydes", 《JOURNAL OF ORGANIC CHEMISTRY》 * |
| MRITUNJOY DATTA等: "N-Phenyl-tert-butanesulfinamide", 《ACTA CRYSTALLOGRAPHICA SECTION E：STRUCTURE REPORTS ONLINE》 * |
| MRITYUNJOY DATTA等: "N-(4-Methoxyphenyl)-tert-butanesulfinamide", 《ACTA CRYSTALLOGRAPHICA SECTION E：STRUCTURE REPORTS ONLINE》 * |
| PRAKASH, ANJANAPPA等: "Efficient indoles and anilines syntheses employing tert-butyl sulfinamide as ammonia surrogate", 《TETRAHEDRON LETTERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725267A (en) * | 2014-04-10 | 2015-06-24 | 申俊 | Method for synthesizing imide compound |
| CN104744290A (en) * | 2014-04-10 | 2015-07-01 | 申俊 | Synthesis method of imide compound |
| CN104744290B (en) * | 2014-04-10 | 2016-07-13 | 申俊 | A kind of synthetic method of imide analog compounds |
| CN106187836A (en) * | 2016-07-01 | 2016-12-07 | 成都理工大学 | Chirality N cinnamyl N phenyl t-butyl sulfenamide and preparation and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Weng et al. | Cooperative effect of silver in copper-catalyzed trifluoromethylation of aryl iodides using Me3SiCF3 | |
| Zhai et al. | Copper-mediated oxidative trifluoromethylthiolation of aryl boronic acids with CF3CO2Na and elemental sulfur | |
| Xin et al. | Synthesis of new planar chiral [2.2] paracyclophane Schiff base ligands and their application in the asymmetric Henry reaction | |
| Pérez Luna et al. | Enantioselective desymmetrization of meso bicyclic hydrazines: a novel approach to the asymmetric synthesis of polysubstituted amino cyclopentanic cores | |
| Pizzuti et al. | Catalytic enantioselective addition of organometallic reagents to N-formylimines using monodentate phosphoramidite ligands | |
| CN106800493A (en) | A kind of method that fragrant nitro is reduced to arylamine | |
| Wang et al. | Synthesis of chiral ferrocenyl aziridino alcohols and use in the catalytic asymmetric addition of diethylzinc to aldehydes | |
| Shi et al. | Acceleration of Petasis reactions of salicylaldehyde derivatives with molecular sieves | |
| Zhao et al. | Enamines: efficient nucleophiles for the palladium-catalyzed asymmetric allylic alkylation | |
| Zhang et al. | Iron‐Catalyzed Cross‐Coupling Reactions for the Construction of Carbon‐Heteroatom Bonds | |
| CN102516138A (en) | N-aryl t-butyl sulfonamide, synthetic method and application thereof | |
| CN111420709A (en) | Application of N-heterocyclic carbene-based mixed nickel (II) complex in reaction for synthesizing 2-linear alkyl benzothiazole compound | |
| Beck et al. | Hydroamination of 1, 1-dimethylallene with primary aryl amines under mild conditions: An atom-economical route to N-(1, 1-dimethyl-2-propenyl)-anilines | |
| Zhao et al. | Activated charcoal supported copper nanoparticles: A readily available and inexpensive heterogeneous catalyst for the N-arylation of primary amides and lactams with aryl iodides | |
| CN104098607A (en) | Complex and application of monophosphine monoazacyclo-carben nickel containing tricyclic hexyl phosphine | |
| Abufarag et al. | A Tripod Ligand with Three Different" Legs" and Some Chiral Zinc Complexes Thereof | |
| Zhao et al. | Regioselective C− H Activation of Toluene with a 1, 2-Bis (N-7-azaindolyl) benzene Platinum (II) Complex | |
| CN109836457B (en) | High-steric-hindrance chiral P, N, N ligand and preparation method and application thereof | |
| Turgut et al. | β-Hydroxyamide derivatives of salicylic acid as organocatalysts for enantioselective reductions of prochiral ketones | |
| Liu et al. | 1, 1-Difluoroethyl chloride (CH 3 CF 2 Cl), a novel difluoroalkylating reagent for 1, 1-difluoroethylation of arylboronic acids | |
| CN103641674B (en) | Method for preparing diaryl sulfone | |
| CN102786537B (en) | Synthesis of economic and stable trifluoromethylthio copper (I) agent | |
| CN110204580A (en) | The nickelous imine composition of the nickeliferous dual bond structure of nitrogen and its preparation and application | |
| CN102503867A (en) | N-aryl-N-alkyl methylpropane-2-sulfinamide and application thereof | |
| CN110305122A (en) | A kind of pyridine ring C4 sulfonyls, the Pybox ligand of phosphorus oxy functional groups and its synthetic method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120627 |