Sciencemadness Discussion Board - styrene -> something interesting

styrene -> something interesting

Polverone - 26-3-2004 at 15:53

I was actually trying to find more information about styrene -> phenylacetamide, but a bunch of other stuff came up too and some was interesting. I don't want to clutter his thread so here it is, in its unedited glory:

Bibliographic Information

Process for preparing phenylacetamide. Zhen, Wenshen. (Peop. Rep.
China). Faming Zhuanli Shenqing Gongkai Shuomingshu (2002), 5 pp.
CODEN: CNXXEV CN 1342644 A 20020403 Patent written in Chinese.
Application: CN 2001-126801 20010918. CAN 138:368619 AN 2003:418028
CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
CN 1342644 A 20020403 CN 2001-126801 20010918

Priority Application
CN 2001-126801 20010918

Abstract

Phenylacetamide is synthesized by the reaction of styrene with S and NH3
at 160° and 35 kg/m2. The molar ratio of styrene to S is 1.9-2.0.

Patent Classifications

Main IPC: C07C233-11. Secondary IPC: C07C231-10.

Indexing -- Section 25-19 (Benzene, Its Derivatives, and Condensed
Benzenoid Compounds)

7704-34-9, Sulfur, uses
Role: CAT (Catalyst use); USES (Uses)
(prepn. of phenylacetamide from styrene)

103-81-1P, Benzeneacetamide
Role: IMF (Industrial manufacture); SPN (Synthetic preparation); PREP
(Preparation)
(prepn. of phenylacetamide from styrene)

100-42-5, Styrene, reactions
_
7664-41-7, Ammonia, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(prepn. of phenylacetamide from styrene)

Supplementary Terms

phenylacetamide prepn styrene sulfur ammonia
***
Bibliographic Information

Selective oxidation of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts. Ma, Ning; Yue, Yinghong; Hua, Weiming; Gao,
Zi. Department of Chemistry, Laboratory of Molecular Catalysis and
Innovative Materials, Fudan University, Shanghai, Peop. Rep. China.
Applied Catalysis, A: General (2003), 251(1), 39-47. CODEN: ACAGE4
ISSN: 0926-860X. Journal written in English. CAN 140:6384 AN
2003:703841 CAPLUS

Abstract

Nanosized spinel-type MgxFe3-xO4 complex oxide catalysts were prepd. by
copptn. and citrate gel methods and were characterized. The crystn. temp.
of spinel particles prepd. by citrate gel method is about 300°C lower than
that of those prepd. by copptn. method. MgxFe3-xO4 catalysts prepd. by
citrate gel method have higher dispersity and smaller particle size,
leading to higher activity for styrene oxidn. with H2O2 as oxidant. The
nonstoichiometric MgxFe3-xO4 catalysts (x<1) are more active for styrene
oxidn. than the pure spinel MgFe2O4. The major reaction (.apprx.65-70
mol%) is oxidative C:C cleavage into benzaldehyde, and the minor reaction
(10 mol%) is epoxidn. and its further isomerization into
phenylacetaldehyde. The effects of solvent, styrene:H2O2 molar ratio,
reaction temp. and time on the conversion and product distribution were
also studied.

Indexing -- Section 45-4 (Industrial Organic Chemicals, Leather, Fats,
and Waxes)
Section cross-reference(s): 67

Epoxidation
Epoxidation catalysts
(selective oxidn. of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts)

100-52-7P, Benzaldehyde, preparation
Role: BYP (Byproduct); PREP (Preparation)
(selective oxidn. of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts)

12068-86-9P, Iron magnesium oxide (Fe2MgO4)
Role: CAT (Catalyst use); IMF (Industrial manufacture); PREP
(Preparation); USES (Uses)
(selective oxidn. of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts)

96-09-3P, Styrene oxide
122-78-1P, Phenylacetaldehyde
Role: IMF (Industrial manufacture); PREP (Preparation)
(selective oxidn. of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts)

100-42-5, Styrene, reactions
_
10377-60-3, Magnesium nitrate
10421-48-4, Ferric nitrate
Role: RCT (Reactant); RACT (Reactant or reagent)
(selective oxidn. of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts)

1309-37-1P, Ferric oxide, preparation
Role: CAT (Catalyst use); IMF (Industrial manufacture); PREP
(Preparation); USES (Uses)
(a-; selective oxidn. of styrene over nanosized spinel-type MgxFe3-xO4
complex oxide catalysts)

Supplementary Terms

epoxidn styrene catalyst spinel benzaldehyde phenylacetaldehyde

Citations

1) Sugimoto, M; J Am Ceram Soc 1999, 82, 269
2) Spretz, R; J Catal 2000, 194, 167
3) Gibson, M; J Catal 1976, 41, 420
4) Xiong, C; Catal Lett 2000, 69, 231
5) Kulkarni, R; J Solid State Chem 1986, 64, 141
6) Chen, Q; Appl Phys Lett 1998, 73, 3156
7) Chen, Q; J Magn Magn Mater 1999, 194, 1
8) Prasad, S; J Alloy Comp 1998, 265, 87
9) Liang, Q; Appl Catal A 1998, 166, 191
10) Yue, Z; Mater Sci Eng B 2001, 86, 64
11) Uzunova, E; Chem Mater 1993, 5, 576
12) Li, J; J Eur Ceram Soc 2001, 21, 39
13) Montouillout, V; J Am Ceram Soc 1999, 82, 3299
14) Verma, A; J Magn Magn Mater 1999, 192, 271
15) Kumar, S; J Catal 1995, 156, 163
16) Zhang, Q; Chem Lett 2001, 946
17) Reddy, J; J Chem Soc, Chem Commun 1992, 1234
***
Bibliographic Information

new preparation of phenylacetic acid. Pan, Zelin; Zhao, Ping. (Peop.
Rep. China). Faming Zhuanli Shenqing Gongkai Shuomingshu (1995), 5
pp. CODEN: CNXXEV CN 1110677 A 19951025 Patent written in Chinese.
Application: CN 94-119654 19941215. CAN 124:316760 AN 1996:285029
CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
CN 1110677 A 19951025 CN 1994-119654 19941215

Priority Application
CN 1994-119654 19941215

Abstract

PhCH2CO2H (I) is prepd. from polystyrene (II). Crushed II was distd. at >
340° to give styrene, which was heated with S and NH4OH in EtOH at 93-95°
to give 94% PhCONH2. Hydrolysis of PhCONH2 with HCl in H2O gave 84% I.
This process is efficient and pollution-free.

Patent Classifications

Main IPC: C07C057-32. Secondary IPC: C07C051-00; C07C051-06;
C07C004-22; C07C231-10.

Indexing -- Section 25-17 (Benzene, Its Derivatives, and Condensed
Benzenoid Compounds)

Depolymerization
(new prepn. of phenylacetic acid)

55-21-0P, Benzamide
100-42-5P, Styrene, preparation
_
Role: IMF (Industrial manufacture); RCT (Reactant); SPN (Synthetic
preparation); PREP (Preparation); RACT (Reactant or reagent)
(new prepn. of phenylacetic acid)

103-82-2P, Phenylacetic acid, preparation
Role: IMF (Industrial manufacture); SPN (Synthetic preparation); PREP
(Preparation)
(new prepn. of phenylacetic acid)

9003-53-6, Polystyrene
Role: RCT (Reactant); RACT (Reactant or reagent)
(new prepn. of phenylacetic acid)

Supplementary Terms

phenylacetic acid prepn; depolymn polystyrene manuf phenylacetic acid;
styrene ammoxidn; benzamide hydrolysis
***
Bibliographic Information

Liquid phase rearrangement of styrene oxide to phenylacetaldehyde
catalyzed by solid acid. Li, Qianhe; Yin, Dulin. Inst. Fine. Catal.
Synth., Hunan Norm. Univ., Peop. Rep. China. Huaxue Tongbao (1994),
(2), 40. CODEN: HHTPAU ISSN: 0441-3776. Journal written in Chinese.
CAN 120:322866 AN 1994:322866 CAPLUS

Abstract

Refluxing styrene oxide with aluminosilicate catalyst SAS-2 in cyclohexane
for 15 min gave 98.2% PhCH2CHO.

Indexing -- Section 25-15 (Benzene, Its Derivatives, and Condensed
Benzenoid Compounds)

Aluminosilicates, uses
Role: CAT (Catalyst use); USES (Uses)
(catalyst, for rearrangement of styrene oxide to phenylacetaldehyde)

Rearrangement catalysts
(solid acid, for styrene oxide to phenylacetaldehyde)

122-78-1P, Phenylacetaldehyde
Role: SPN (Synthetic preparation); PREP (Preparation)
(prepn. of, from styrene oxide, solid acid catalyst for)

96-09-3, Styrene oxide
Role: RCT (Reactant); RACT (Reactant or reagent)
(rearrangement of, solid acid catalyst for)

Supplementary Terms

styrene oxide rearrangement catalyst solid acid; phenylacetaldehyde
***
Bibliographic Information

Selective oxidation of styrene and its derivatives in the presence of
orthophosphoric acid esters. Kijenski, Jacek; Ruszczynski, Jerzy;
Glinski, Marek. Wydz. Chem., Politech. Warsazawskiej, Warsaw, Pol.
Przemysl Chemiczny (1994), 73(2), 54-8, 42. CODEN: PRCHAB ISSN:
0033-2496. Journal written in Polish. CAN 120:220812 AN
1994:220812 CAPLUS

Abstract

A selective method of oxidn. of styrene and its derivs. in the liq. phase
in the presence of phosphoric acids esters is presented. At low reaction
temp. (55-70°), styrene, 4-methylstyrene, and a-methylstyrene gave
corresponding carbonyl compds. At elevated temps., styrene oxide,
phenylacetic aldehyde, and phenylethanediol monobenzoate were found among
the reaction products of styrene oxidn. The probable of action of
phosphoric acid esters was detd., based on the 1H NMR and 31P NMR data.
The usefulness of the proposed method for large-scale oxidn. of styrene
was shown.

Indexing -- Section 45-4 (Industrial Organic Chemicals, Leather, Fats,
and Waxes)
Section cross-reference(s): 25

Oxidation
(of styrene, in presence of phosphoric acid esters, mechanism of)

Oxidation catalysts
(phosphoric acid esters, for styrene)

78-40-0, Triethyl phosphate
126-73-8, Tributyl phosphate, uses
1330-78-5, Tritolyl phosphate
Role: CAT (Catalyst use); USES (Uses)
(catalysts, for styrene oxidn.)

98-83-9, reactions
100-42-5, reactions
_
622-97-9, 4-Methylstyrene
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxidn. of, in presence of phosphoric acid ester catalysts)

96-09-3P, Styrene oxide
122-78-1P, Phenylacetic aldehyde
154397-49-6P
Role: IMF (Industrial manufacture); PREP (Preparation)
(prepn. of, by oxidn. of styrene in presence of phosphoric acid ester
catalysts)

Supplementary Terms

oxidn styrene phosphoric acid ester; catalyst phosphoric ester oxidn styrene
***
Bibliographic Information

Manufacture of oxygen-containing derivatives of ethylbenzene with Candida
maltosa. Repp, Hans Dieter; Stottmeister, Ulrich; Doerre, Marina;
Haufe, Guenter; Weber, Lutz. (Akademie der Wissenschaften der DDR,
Germany). Ger. (East) (1991), 3 pp. CODEN: GEXXA8 DD 295188 A5
19911024 Patent written in German. Application: DD 90-341789
19900619. CAN 116:127019 AN 1992:127019 CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
DD 295188 A5 19911024 DD 1990-341789 19900619

Priority Application
DD 1990-341789 19900619

Abstract

The title compds. are prepd. by cultures of n-alkane-utilizing C. maltosa
grown under non-sterile conditions. C. maltosa cultured on medium contg.
C8-20 n-alkanes and styrene produced styrene oxide, Ph acetic acid,
phenylacetaldehyde, acetophenone, phenylethanol, etc.

Patent Classifications

IPC: C12P007-02; C12P007-40; C12P007-26; C12R001-72.

Indexing -- Section 16-5 (Fermentation and Bioindustrial Chemistry)

Candida maltosa
(ethylbenzene or styrene oxidn. products manuf. with, under
non-sterile conditions)

Fermentation
(ethylbenzene or styrene oxidn. products, with Candida maltosa, under
non-sterile conditions)

Alkanes, uses
Role: USES (Uses)
(in manuf. ethylbenzene or styrene oxidn. products manuf. with Candida
maltosa under non-sterile conditions)

60-12-8P, 2-Phenylethanol
90-64-2P, Mandelic acid
96-09-3P, Styrene oxide
98-85-1P, 1-Phenylethanol
98-86-2P, Acetophenone, preparation
103-82-2P, Phenyl acetic acid, preparation
122-78-1P, Phenylacetaldehyde
122-99-6P
611-73-4P, Phenyl gloxylic acid
1074-12-0P, Phenyl glyoxal
Role: BMF (Bioindustrial manufacture); BIOL (Biological study); PREP
(Preparation)
(manuf. of, from styrene, with Candida maltosa cultured under
non-sterile conditions)

100-41-4DP, Ethylbenzene, oxidn. products
Role: BMF (Bioindustrial manufacture); BIOL (Biological study); PREP
(Preparation)
(manuf. of, with Candida maltosa cultured under non-sterile conditions)

100-41-4, Ethylbenzene, reactions
100-42-5, Styrene, reactions
_
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxidn. of, with Candida maltosa cultured under non-sterile conditions)

Supplementary Terms

ethylbenzene oxygen deriv manuf Candida; styrene oxygen deriv manuf Candida
***
Bibliographic Information

Phenylacetaldehyde. (Kuraray Co., Ltd., Japan). Jpn. Kokai Tokkyo
Koho (1982), 6 pp. CODEN: JKXXAF JP 57091945 A2 19820608 Showa.
Patent written in Japanese. Application: JP 80-168748 19801128.
CAN 97:144575 AN 1982:544575 CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
JP 57091945 A2 19820608 JP 1980-168748 19801128

Priority Application
JP 1980-168748 19801128

Abstract

PhCH2CHO (I) was prepd. by oxidn. of styrene with sulfolane over Pd or its
salts and CuCl2 in H2O and org. solvents. Thus, a mixt. PdCl2 35.5,
CuCl2.2H2O 93.8, CuCl 4.95, and sulfolane 550 g in H2O and mesitylene was
heated at 75° under N, 46.8 g styrene added, and the mixt. stirred 25 min
to give 29.0 g distillate contg. I 86, MeCOPh 13, and others 1 wt. %.

Patent Classifications

IPC: C07C047-228; C07C045-28. Additional IPC: B01J023-42; B01J027-10.

Indexing -- Section 25-15 (Benzene, Its Derivatives, and Condensed
Benzenoid Compounds)

Oxidation
(of styrene with sulfolane, phenylacetaldehyde from)

7647-10-1
Role: RCT (Reactant); RACT (Reactant or reagent)
(catalysts contg. copper chloride and, for oxidn. of styrene)

7447-39-4, uses and miscellaneous
7758-89-6
Role: CAT (Catalyst use); USES (Uses)
(catalysts, contg. palladium chloride and, for oxidn. of styrene)

98-86-2P, preparation
Role: FORM (Formation, nonpreparative); PREP (Preparation)
(formation of, in oxidn. of styrene)

100-42-5, reactions
_
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxidn. of)

122-78-1P
Role: SPN (Synthetic preparation); PREP (Preparation)
(prepn. of)

Supplementary Terms

styrene oxidn; phenylacetaldehyde
***
Bibliographic Information

Styrene. Huang, I-Der. (Exxon Research and Engineering Co., USA).
Ger. Offen. (1977), 24 pp. CODEN: GWXXBX DE 2719840 19771124
Patent written in German. Application: DE 77-2719840 19770504. CAN
90:122238 AN 1979:122238 CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
DE 2719840 A1 19771124 DE 1977-2719840 19770504
GB 1583091 A 19810121 GB 1977-15544 19770414
AU 7724320 A1 19781019 AU 1977-24320 19770415
AU 506781 B2 19800124
CA 1081714 A1 19800715 CA 1977-276229 19770415
ZA 7702364 A 19780329 ZA 1977-2364 19770419
NL 7705003 A 19771114 NL 1977-5003 19770506
JP 52136133 A2 19771114 JP 1977-53003 19770509
FR 2351072 A1 19771209 FR 1977-14114 19770509
FR 2351072 B1 19831014
BR 7703000 A 19780208 BR 1977-3000 19770509
BE 854440 A2 19771110 BE 1977-55892 19770510
US 4350825 A 19820921 US 1980-156067 19800530

Priority Application
US 1976-685057 19760510
US 1976-755245 19761229
US 1978-960735 19781115

Abstract

Styrene [100-42-5] is manufd. by catalytically oxidizing toluene
[108-88-3] and AcOH [64-19-7] or propionic acid [79-09-4] to give an
oxidn. product contg. benzyl acetate [140-11-4] or benzyl propionate
[122-63-4], treating this compn. with a CO-contg. gas in the presence of a
carbonylation catalyst to form phenylacetic acid [103-82-2],
hydrogenating to form phenethyl alc. [60-12-8], and dehydrating. This
process provides an alternative to styrene manuf. from benzene and
ethylene, and all steps give good conversion and selectivity.

Patent Classifications

IPC: C07C015-10.

Indexing -- Section 35-2 (Synthetic High Polymers)
Section cross-reference(s): 25

122-63-4
140-11-4
Role: RCT (Reactant); RACT (Reactant or reagent)
(carbonylation of)

60-12-8
Role: RCT (Reactant); RACT (Reactant or reagent)
(dehydration of)

64-19-7, reactions
79-09-4, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(esterification by, of oxidized toluene)

103-82-2, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(hydrogenation of)

100-42-5P, preparation
_
Role: IMF (Industrial manufacture); PREP (Preparation)
(manuf. of, 4-step process for)
***
Bibliographic Information

Hydrolysis of chlorinated styrene - a new route for the synthesis of
phenylacetic acid and a-ethoxyphenylacetic acid. Lanchow University,
Dep. Chem., Lanchow, Peop. Rep. China. Huaxue Xuebao (1976),
34(4), 295-300. CODEN: HHHPA4 ISSN: 0567-7351. Journal written in
Chinese. CAN 88:104848 AN 1978:104848 CAPLUS

Abstract

Chlorination of styrene in the presence of Bz2O2 at 100-10° gave 12
chlorinated products, which on alk. hydrolysis in alc. gave PhCH2CO2H,
PhCH(OEt)CO2H and BzOH in 56-63, 7 and 0.6% yield, resp. Chlorination of
PhEt gave similar products, and esterification of the crude acidic
products gave 53.4% PhCH2CO2Et.

Indexing -- Section 25-17 (Noncondensed Aromatic Compounds)

Chlorination
(of styrene and ethylbenzene)

Hydrolysis
(alk., of chlorostyrene and chloroethylbenzene)

100-41-4, reactions
100-42-5, reactions
_
Role: RCT (Reactant); RACT (Reactant or reagent)
(chlorination of)

4714-28-7P
19676-39-2P
Role: RCT (Reactant); SPN (Synthetic preparation); PREP (Preparation);
RACT (Reactant or reagent)
(prepn. and hydrolysis of)

103-82-2P, preparation
33224-99-6P
65792-30-5P
Role: SPN (Synthetic preparation); PREP (Preparation)
(prepn. of)

Supplementary Terms

phenylacetic acid; ethoxyphenylacetic acid; hydrolysis chlorostyrene;
chlorination styrene ethylbenzene
***
Bibliographic Information

The Etard reaction. IV. Oxidation of ethylbenzene with chromyl chloride.
Rentea, C. N.; Rentea, Marina; Necsoiu, Ileana; Nenitzescu, C. D.
Inst. Org. Chem., Bucharest, Rom. Revue Roumaine de Chimie (1967),
12(12), 1495-501. CODEN: RRCHAX ISSN: 0035-3930. Journal written in
English. CAN 69:2591 AN 1968:402591 CAPLUS

Abstract

The Etard complex of ethylbenzene (I) was prepd. in CCl4 at 0°. Decompn.
of the Etard complex of I by water yielded phenylacetaldehyde (II) and
acetophenone (III) in equal proportions, along with styrene and BzH. The
same products were obtained by treatment of styrene with chromyl chloride
and hydrolysis of the complex, II being the major product. Chromyl
chloride oxidn. of epoxyphenylethane yielded BzH and II and a trace of
III. Presumably all these compds. result from a common intermediate
possessing an epoxide-like structure. The mechanism of these reactions is
discussed.

Indexing -- Section 25 (Noncondensed Aromatic Compounds)

Etard reaction
(with (epoxyethyl)benzene and ethylbenzene and styrene, mechanism of)

14977-61-8
Role: RCT (Reactant); RACT (Reactant or reagent)
(in oxidn. of (epoxyethyl)benzene, ethylbenzene and styrene, mechanism
of)

96-09-3
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxidn. of, with dichlorodioxochromium, acetophenone and benzaldehyde
from, mechanism of)

100-41-4, reactions
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxidn. of, with dichlorodioxochromium, acetophenone and
phenylacetaldehyde from mechanism of)

100-42-5, reactions
_
Role: RCT (Reactant); RACT (Reactant or reagent)
(oxidn. of, with dichlorodioxochromium, acetophenone and
phenylacetaldehyde from, mechanism of)

Supplementary Terms

ethylbenzene oxidn
***
Bibliographic Information

Essential oils. CCII. Synthesis of phenylacetaldehyde from styrene.
Naves, Yves R. Lab. Rech. Givaudan S.A., Vernier-Geneva, Switz.
Helvetica Chimica Acta (1967), 50(1), 319-21. CODEN: HCACAV ISSN:
0018-019X. Journal written in French. CAN 66:94771 AN 1967:94771
CAPLUS

Abstract

cf. CA 66, 11054w. A mixt. of 1400 g. 77% HCO2H and 208 g. styrene at
30-40° was treated with 285 g. 30% H2O2 in 30 min., the mixt. was stirred
at 30° for 2 hrs., excess HCO2H and water were eliminated in vacuo, and
the residue was distd. to give 81% phenylethylene glycol monoformate (I),
b1.7 129-30°, d20 1.1777, n20D 1.52608. I (10 g.) was oxidized with 40 g.
HNO3 (d. 1.36) with cooling and the mixt. was neutralized with K2CO3,
extd. with ether, and boiled for 6 hrs. in 100 ml. water. The product was
neutralized as above, treated with ether in a percolator, and sublimed at
1 mm. to give the phenacyl alc., which gave benzaldehyde upon treatment
with 2% NaOH. A mixt. of 100 g. crude I and 200 g. 15% NaOH was heated at
60° for 2 hrs., neutralized with CO2 and extd. with ether to give an 85%
yield of the sapon. product (II), m. 67-8° (1:1 C6H6-petroleum ether). A
mixt. of 100 g. I and 300 ml. 25% H2SO4 was heated to boiling with
continuous removal of water and after 16 hrs., 52 g. of a non-aq.
distillate was sepd., which was dried and distd. to give 43.2 g.
phenylacetaldehyde and 3.5 g. 2-phenylnaphthalene, m. 101.5-2.0°. A mixt.
of 100 g. II and 300 ml. 25% H2SO4 was treated as above to give 66.2 g.
phenylacetaldehyde, b2.2 59-60°, d20 1.0273, n20D 1.52480.

Indexing -- Section 25 (Noncondensed Aromatic Compounds)

100-42-5, uses and miscellaneous
_
Role: RCT (Reactant); RACT (Reactant or reagent)
(phenylacetaldehyde prepn. from)

122-78-1P
Role: SPN (Synthetic preparation); PREP (Preparation)
(prepn. from styrene)

93-56-1P
612-94-2P
15507-46-7P
Role: SPN (Synthetic preparation); PREP (Preparation)
(prepn. of)

Supplementary Terms

STYRENES; ACETALDEHYDES PHENYL
***
Bibliographic Information

Phenylacetaldehyde. (Deutsche Gold- und Silber-Scheideanstalt vorm.
Roessler). (1956), GB 761040 19561107 Patent language
unavailable. CAN 51:66783 AN 1957:66783 CAPLUS

Patent Family Information

Patent No. Kind Date Application No. Date
GB 761040 19561107 GB
DE 1069609 DE

Abstract

Aluminum and (or) iron oxides are used as catalysts to convert styrene
oxide to phenylacetaldehyde at 170° practically quantitatively.

Indexing -- Section 10 (Organic Chemistry)

122-78-1, Acetaldehyde, phenyl-
(prepn. of)

Organikum - 26-3-2004 at 18:35

For my personal taste the crux is that one utmost always ends up with phenylacetaldehyde - a compound which plain lacks a carbon on the chain.
Sulfur and NH3 seem to convince the styrene to change to something else. But this stinks.
On the other side also this ultrastinky phenylacetic acid stuff lacks a carbon on the chain which can miracously be attached by bumming the stink and acetic acid through a hot tube with Mg-catalyst on pumice to end up with something what smells better
and has a carbon more.

Should it really be impossible to bumm styrene and compound X through a tube to end up with the same product one gets with stink and GAA? Or at least with the related alcohol instead of the ketone? Even a alpha-hydroxy compound might be a considerable variation worth the effort.

Question:
- how to get styrene-oxide/glycol/diol/? from styrene?
Suggestion:
- if this is easy - what about running this search again with the named compounds?

And no dirty words this time! "Nanosized-spinel type" Ha! I know this!

Polverone - 29-3-2004 at 17:35

Quote:

Question:
- how to get styrene-oxide/glycol/diol/? from styrene?
Suggestion:
- if this is easy - what about running this search again with the named compounds?

The answer to part 1 can be found in this extensive review article: <A HREF="http://www.sciencemadness.org/papers/monomeric_styrenes.pdf">The Reactions of Monomeric Styrenes</A>. I will have to wait a bit until I can answer part 2 of your question.

[Edited on 3-30-2004 by Polverone]

Organikum - 29-3-2004 at 19:27

Meanwhile I discovered that there is a possibility to get this missing carbon onto the sidechain of phenylacetaldehyde by dimethylzinc or dimethylcadmium what forms the realted ketone - but both compounds are not really nice ones as a quick look into the MERCK showed, but I will have to look deeper into this before I can tell more....
The reaction is told to be high-yielding though.

JohnWW - 19-9-2004 at 02:26

About styrene (phenylethylene): none of the above posts adequately address the possibility of the various catalytic oxidation reactions of styrene competing with catalytic or free-radical polymerization to solid polystyrene. This has the potential to seriously reduce yields.

According to textbooks, a common laboratory oxidation method for alkenes having a terminal =CH2 group, including styrene, to the corresponding aldehydes, is the Wacker oxidation. This is a heterogenous reaction, which in the case of styrene would involve two liquid phases and a gas phase, involving reaction with PdCl2, CuCl2, air/oxygen, and aqueous HCl, which would have to be shaken together for a while in a closed vessel. It has a three-step mechanism, with reaction with H2O to produce the aldehyde, reduction of the PdCl2 to Pd then re-formation of PdCl2, and reduction of the CuCl2 to CuCl then reoxidation with O2.

John W.

Reverend Necroticus Rex - 19-9-2004 at 18:32

Post 510625, Shane_Warne, the hive, pyrolysis of polystyrene to it's monomer via S, NH3aq and EtOH, then conversion to phenyl-2-propanone from phenylacetic acid

JohnWW - 19-9-2004 at 21:59

Pyrolysis of polystyrene to its monomer, with those reagents, is likely to be incompatible with, or at least seriously compromise, any oxidation reaction that one is trying to carry out on styrene.

BTW What is the URL of "the hive" site, which I presume is another forum, to which you refer?

John W.

UpNatom - 20-9-2004 at 06:01

I haven't read it but I suspect that is supposed to be pyrolysis of polymer to monomer first then the Willgerodt-Kindler.

Reverend Necroticus Rex - 20-9-2004 at 07:06

Yes I did mean pyrolysis of the polymer first, and the URL is www.the-hive.ws.

UTFSE there for the post I mentioned, I think there are a few other experimentals and discussions concerning polystyrene/styrene monomer that might bee of interest.

Aba hallo !!

Organikum - 13-11-2004 at 13:12

I reread Polverones post and found this what I have overlooked before:

Quote:

Hydrolysis of chlorinated styrene - a new route for the synthesis of phenylacetic acid and a-ethoxyphenylacetic acid. Lanchow University, Dep. Chem., Lanchow, Peop. Rep. China. Huaxue Xuebao (1976), 34(4), 295-300. CODEN: HHHPA4 ISSN: 0567-7351. Journal written in Chinese. CAN 88:104848 AN 1978:104848 CAPLUS

Abstract:
Chlorination of styrene in the presence of Bz2O2 at 100-10° gave 12 chlorinated products, which on alk. hydrolysis in alc. gave PhCH2CO2H, PhCH(OEt)CO2H and BzOH in 56-63, 7 and 0.6% yield, resp. Chlorination of PhEt gave similar products, and esterification of the crude acidic products gave 53.4% PhCH2CO2Et.

This sounds to me VERY similar to the wellknown toluene chlorination, I guess UV can replace the benzoylperoxide, like catalytic amounts of red phosphorus.
About 50% of PAA sounds very ok to me, avoiding the stink of hell and the H2S the Willgerodt produces. Chlorine is comparable simple to handle.
Suggested workup: The alk. hydrolysis produces a salt, so reducing the volume and washing with benzene/toluene or chloroform/DCM should remove most impurities, acidifying and extracting with a chlorinated solvent to get the PAA pure enough (as I hope) for further uses.

Stupid question: "alk. hydrolysis in alc." says hydrolysis with alkali in alcohol, does this say alcohol pure or a mixture of water/alcohol is to be used? I would say a mixture, but I better ask, org. chemistry is sometimes odd.....

How could I have overlooked this?
tz, tz....

/ORG

Organikum - 16-11-2004 at 11:00

A friend sent me the chinese article in question and I extracted two drawings from it.

Here they are:

It shows that the reaction proceeds by chlorination of the styrene to alpha-beta-beta trichloroethylbenzene which undergoes several steps of dehydrohalogenation by hydrolysis followed and finally hydrogenolyis to phenylacetic acid.
Thats at least how it looks to me.
Doesnt say that I understand it - I do not.

Anybody able to speak some words of wisdom on this is welcome to do so.

The second drawing shows the reaction of alpha-alpha-beta-beta- tetrachloroethylbenzene a byproduct of the chlorination when it undergoes hydrolysis.

This would say for the procedure of the dehydrogenolysis/hydrolysis that a solution of NaOH or KOH in fairly pure alcohol is used first, followed by addition of a good amount of water+base and further refluxing.
At least I hope so.

[Edited on 16-11-2004 by Organikum]

trilobite - 21-11-2004 at 16:04

Wow... that's interesting. I think the hydrolysis part is quite hard to fuck up if one has any idea about what he is doing.

I would use a healthy excess of KOH in ethanol with sufficient water added for hydrolysis of the phenylketene. KOH because it is more soluble in alcohols than NaOH.

Looking at the first scheme it appears that there is enough water provided to hydrolyse the phenylketene, ethyl phenylacetate (probable reaction intermediate, from phenylketene + EtOH) and the other products from the chlorination. Of course, the ester will be hydrolysed anyway with the proposed addition of water and hydroxide, but it could turn out to be unneeded trouble. The presence of water reduces possible side reactions with the ethoxide ion, such as the one in the second scheme.

The two eliminations (dehydrohalogenations) are most likely very fast reactions. Especially the first molecule is just asking for it, with a chlorine on a benzylic secondary carbon, a proton on a carbon with two chlorines (acidic, think: OH(-) + HCCl3 --> H2O + (-)CCl3 ) and the resulting aromatic conjugation. After that, the transition states for all the following reactions are stabilised by aromatic conjugation, so those reactions should be relatively fast too.

manimal - 20-10-2009 at 18:02

Quote:

Chlorination of styrene in the presence of Bz2O2 at 100-10° gave 12
chlorinated products, which on alk. hydrolysis in alc. gave PhCH2CO2H,
PhCH(OEt)CO2H and BzOH in 56-63, 7 and 0.6% yield, resp. Chlorination of
PhEt gave similar products, and esterification of the crude acidic
products gave 53.4% PhCH2CO2Et.

I wonder if the so-called "Loomis method" of chlorinating toluene w/ hypochlorite could be applied to stryrene.

TIETSE - 21-10-2009 at 11:06

manimal look this pdf

Attachment: The Willgerodt and Kindler Reactions..pdf (595kB)
This file has been downloaded 1720 times

manimal - 21-10-2009 at 19:17

I'm already well aware of the Willgerodt reaction.

What I was asking was, if hypochlorite can induce free-radical chlorination of toluene, what obstructions are there that would prevent it from inducing free-radical chlorination of styrene (which is what the abstract provided by Polverone suggests to do)?

[Edited on 22-10-2009 by manimal]

manimal - 15-8-2010 at 02:00

Quote:

It is important that the right hydrolysis conditions be implemented in this case. According to http://www.google.com/patents?hl=en&lr=&vid=USPAT289..., and 'Reactions of monomeric styrenes', too strong of an alkali causes dehydrohalogenation of 1,2,2 trichloroethylbenzene to 1,2 dichlorostyrene, which can undergo further hydrolysis to phenacyl chloride, rather than to phenylacetic acid.

[Edited on 15-8-2010 by manimal]

manimal - 20-1-2011 at 15:30

Quote:

Attachment: lunwen.pdf (90kB)
This file has been downloaded 1151 times

manimal - 21-1-2011 at 03:50

I don't understand the above document. Apparently, it is an "improved method" over the previous method, whereby the styrene is chlorinated at 30C without a catalyst, but the machine translation is mostly unintelligible.